Heteroarylphthalides

ABSTRACT

3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)-phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of our copending applicationSer. No. 027,031, filed Apr. 4, 1979 and now U.S. Pat. No. 4,251,446which issued on Feb. 17, 1981, in turn a continuation-in-part of ourcopending application Ser. No. 868,583, filed Jan. 11, 1978 and now U.S.Pat. No. 4,189,171 which issued on Feb. 19, 1980, in turn acontinuation-in-part of our application Ser. No. 773,180, filed Mar. 1,1977 and now abandoned.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to novel compounds classified in the field oforganic chemistry as 3-aryl-3-heteroarylphthalides and3,3-bis(heteroaryl)phthalides useful as color precursors, particularlyin the art of carbonless duplicating as, for example, inpressure-sensitive systems, in thermal marking systems and inhectographic or spirit-reproducing copying systems; to substituted2-(indolylcarbonyl)benzoic acids and 2-(pyrrolylcarbonyl)benzoic acidsuseful as intermediates to the subject phthalide color precursors; toprocesses for preparing said phthalides and benzoic acids; and topressure-sensitive duplicating systems, thermal marking systems andhectographic copying systems containing the same.

(b) Description of the Prior Art

Several classes of organic compounds of widely diverse structural typesare known to be useful as colorless precursors for carbonlessduplicating systems. Among the more important classes, there may benamed phenothiazines, for example, benzoyl leuco methylene blue;phthalides with which this invention is concerned, for example, crystalviolet lactone; fluorans, for example, 2'-anilino-6'-diethylaminofluoranand 2'-dibenzylamino-6'-diethylaminofluoran; and various other types ofcolorless precursors currently employed in commercially acceptedcarbonless copy systems. Typical of the many such systems taught in theprior art are those described in U.S. Pat. Nos. 2,712,507, 2,800,457 and3,041,289 which issued July 5, 1955, July 23, 1957 and June 26, 1962,respectively. Many of the color formers in the prior art suffer one ormore disadvantages such as low tinctorial strength, poor lightstability, low resistance to sublimation, low susceptibility tocopiability of the color-developed form in standard copying machines,for example, a Xerox copier, and low solubility in common organicsolvents, the latter disadvantage thus requiring the use of specializedand expensive solvents in order to obtain microencapsulated solutions ofsufficient concentration for use in pressure-sensitive copying systems.

The following items to date appear to constitute the most relevant priorart with regard to the instant invention.

U.S. Pat. No. 3,491,112, issued Jan. 20, 1970 discloses in mostpertinent part a series of normally colorless phthalides stated to beuseful as color formers in pressure-sensitive copying paper which arerepresented by the structural formula ##STR1## wherein ##STR2## is aheterocyclic radical selected from the group consisting of ##STR3## inwhich R₁ and R₂ are C₁ to C₄ alkyl, phenyl and hydrogen; Z and Y arehydrogen and dialkylamino in which alkyl is C₁ to C₄ alkyl with theproviso that only one Z and Y can be said dialkylamino while the otheris hydrogen; and R₃ and R₄ are C₁ to C₄ alkyl.

U.S. Pat. No. 3,779,753, issued Dec. 18, 1973 discloses the phthalidehaving the formula ##STR4## which is stated to be useful as an opticalfilter agent "in photographic processes to protect a selectively exposedphotosensitive material from further exposure during processing in thepresence of incident light.

British Pat. No. 1,427,318, published Mar. 10, 1976, discloses theinteraction of trimellitic anhydride and m-diethylaminophenol to obtaina mixture of 4-diethylamino-2-hydroxybenzophenone-2',4'-dicarboxylicacid and the corresponding 2',5'-dicarboxylic acid isomer. The isomericmixture is then interacted with 3,5-dimethylphenol in the presence ofsulfuric acid followed by treatment with sodium hydroxide to obtain thecompound having the structure ##STR5## which is stated to be useful as acolor former in a spirit reproducing process.

U.S. Pat. No. 3,491,116, issued Jan. 20, 1970 discloses in mostpertinent part a series of normally colorless phthalides ##STR6##wherein R₁ and R₂ comprise alkyl radicals having from one to five carbonatoms, aryl radicals and hydrogen; and R₃ and R₄ comprise alkyl radicalshaving from one to five carbon atoms and hydrogen.

U.S. Pat. No. 3,509,173, issued Apr. 28, 1970 discloses in mostpertinent part a series of normally colorless phthalides ##STR7##wherein R₁ and R₂ consist of alkyl radicals having fewer than fivecarbon atoms, phenyl radicals and hydrogen.

U.S. Pat. No. 3,509,174, issued Apr. 28, 1970, discloses1,2-dimethyl-3-(2-carboxybenzoyl)indole which is stated to be anintermediate to a series of 3,3-bis(3-indolyl)phthalides useful as colorformers in pressure-sensitive copying paper.

SUMMARY OF THE INVENTION

The present invention provides novel 3-aryl-3-heteroarylphthalidesselected from among 3-aryl-3-indolylphthalides,3-aryl-3-pyrrolylphthalides, 3-aryl-3-carbazolylphthalides and3,3-bis(heteroaryl)phthalides, particularly 3,3-bis(indolyl)phthalideswhich are useful as color formers in pressure-sensitive duplicatingsystems, in thermal marking systems and in hectographic orspirit-reproducing systems. The compounds develop colored images of goodto excellent tinctorial strength, and have the advantages of improvedlight stability, high resistance to sublimation and enhanced solubilityin common organic solvents. Certain species are also soluble in waterand lower alcohols and are therefore of particular utility as colorformers in hectographic or spirit-reproducing copying systems. Thepresent invention also provides 2-heteroarylcarbonyl benzoic acidsuseful as intermediates to the subject phthalide color formers.

In one of its composition of matter aspects the invention relates to aseries of 3-aryl-3-heteroaryl-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides and3,3-bis(heteroaryl)-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides which areuseful as color formers in pressure-sensitive carbonless duplicatingsystems, thermal marking systems or hectographic copying systems.

In a second of its composition of matter aspects, the invention relatesto certain 2-heteroaryl-carbonyl-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoicacids which are useful as intermediates for the preparation of thephthalide final products of the invention.

In one of its process aspects, the invention relates to a process forpreparing a 3-X-3-Z-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalide which comprisesinteracting a 2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acidwith a 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6') -2-R^(5') -5/6-Y^(1')-indole.

In a second process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-aminophthalide which comprises reducing thecorresponding 3-X-3-Z-5/6-nitrophthalide.

In a third process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-acetamidophthalide which comprises interactingthe appropriate 2-(X-carbonyl)-5/6-aminobenzoic acid with a 3-R⁴-N,N-(R)₂ -aniline or a 1-R^(6') -2-R^(5') -5/6-Y^(1') -indole in thepresence of acetic anhydride.

In a fourth process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-COOY-phthalide which comprises esterifying thecorresponding 3-X-3-Z-5/6 carboxyphthalide with an appropriatealkylating agent in the presence of an alkali.

In a fifth process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-CONY'Y"-phthalide which comprises amidating thecorresponding 3-X-3-Z-5/6-carboxyphthalide with the appropriate compoundof the formula HNY'Y".

In a sixth process aspect, the invention relates to a process forpreparing a 3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalide in which R⁵═R^(4'), R⁶ ═R^(6') and Y¹ ═Y^(1') which comprises interacting a 3-R^(o)-4-R¹ -5-R² -6-R³ -phthalic anhydride with approximately two molecularproportions of a 1-R⁶ -2-R⁵ -5/6-Y¹ -indole.

In a seventh process aspect, the invention relates to a process forpreparing a 2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ benzoic acid whichcomprises interacting a 3-R^(o) -4-R¹ -5-R² -6-R³ -phthalic anhydridewith a 1-R⁶ -2-R⁵ -5/6-Y¹ -indole or a 1-R⁷ -pyrrole.

In an eighth process aspect, the invention relates to a process forpreparing a 2-(X-carbonyl)-5/6-aminobenzoic acid which comprisesreducing the corresponding 2-(X-carbonyl)-5/6-nitrobenzoic acid.

The present invention provides as articles of manufacturepressure-sensitive carbonless duplicating systems, thermal markingsystems and hectographic copying systems each containing a color-formingsubstance comprising a 3-aryl-3-heteroaryl-4-R^(o) -5-R¹ -6-R² -7-R³-phthalide or a 3,3-bis(heteroaryl)-4-R^(o) -5-R¹ -6-R² -7-R³-phthalide.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention, in its composition of matter aspectsrelating to the final products, resides in the novel phthalides, whichare particularly useful as colorless precursors in the art of carbonlessduplicating, thermal marking and hectograph duplicating, and which areselected from the group consisting of 3-X-3-Z-4-R^(o) -5-R¹ -6-R² -7-R³-phthalides having the formula ##STR8## wherein R^(o), R¹, R² and R³each represent hydrogen or halo or when R^(o), R³ and one of R¹ and R²are each hydrogen, the other of R¹ and R² represents nitro, amino,acetamido, dialkylamino wherein alkyl is non-tertiary C₁ to C₄ alkyl or##STR9## in which B represents ##STR10## wherein Y is hydrogen, analkali metal cation, an ammonium cation, a C₁ to C₁₈ mono-, di- ortrialkylammonium cation, C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, benzyl orbenzyl substituted in the benzene ring thereof by C₁ to C₁₂ alkyl, haloor C₁ to C₈ alkoxy, Y' is hydrogen or C₁ to C₁₈ alkyl, and Y" ishydrogen, C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dialkylaminoalkyl; Xrepresents a monovalent moiety selected from the class having theformulas ##STR11## Z represents a monovalent moiety selected from theclass having the formulas ##STR12## where, in the above, R representsnon-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl, R⁴ represents acetamido,dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, C₂ to C₅acyloxy, and when one of R¹ or R² represents any of said carboxy or saidcarbonyl substituents, R⁴ further represents hydrogen, C₁ to C₃ alkyl,C₁ to C₄ alkoxy or halo, R⁵ and R^(5') represent hydrogen, C₁ to C₃alkyl or phenyl, R⁶ and R^(6') represent hydrogen, C₁ to C₁₈ alkyl, C₂to C₄ alkenyl, benzyl or benzyl substituted in the benzene ring by oneor two of halo or C₁ to C₃ alkyl, R⁷ and R⁸ represent hydrogen, C₁ to C₃alkyl or phenyl, and Y¹ and Y^(1') represent one or two of hydrogen, C₁to C₃ alkyl, C₁ to C₃ alkoxy, halo or nitro with the provisos (i) that Xand Z can both simultaneously represent monovalent indolyl moieties onlywhen at least one of R¹ and R² represent said ##STR13## and (ii) Xrepresents a pyrrolyl or a carbazolyl moiety only when Z represents a2-R⁴ -4-N(R)₂ -phenyl moiety.

In a first particular embodiment in accordance with its final productcomposition of matter aspect, the invention sought to be patentedresides in the novel 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-X-4-R^(o) -5-R¹ -6-R²-7-R³ -phthalides of Formula I wherein Z is 2-R⁴ -4-N(R)₂ -phenyl andare of the formula ##STR14## wherein R, R^(o), R¹, R², R³, R⁴ and X eachhave the same respective meanings given in relation to Formula I.Preferred compounds within the ambit of this particular embodiment are:the novel 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides of Formula IIwherein X is 1-R⁶ -2-R⁵ -5/6-Y¹ -3-indolyl according to the formula##STR15## wherein R, R^(o), R¹, R², R³, R⁴, R⁵, R⁶ and Y¹ each have thesame respective meanings given in relation to Formula II; the novel3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(1-R⁷ -2-pyrrolyl)-4-R^(o) -5-R¹ -6-R² -7-R³-phthalides of Formula II wherein X is 1-R⁷ -2-pyrrolyl according to theformula ##STR16## wherein R, R^(o), R¹, R², R³, R⁴ and R⁷ each have thesame respective meanings given in relation to Formula II; and the novel3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(9-R⁸ -3-carbazolyl)-4-R^(o) -5-R¹ -6-R²-7-R³ -phthalides of Formula II wherein X is 9-R⁸ -3-carbazolylaccording to the formula ##STR17## wherein R, R^(o), R¹, R², R³, R⁴ andR⁸ each have the same respective meanings given in relation to FormulaII.

A particularly preferred group of 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(9-R⁸-3-carbazolyl)-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides among thoserepresented by Formula V are those wherein R^(o), R¹, R² and R³ eachrepresent hydrogen or halo or when R^(o), R³ and one of R¹ and R² areeach hydrogen, the other of R¹ and R² represents ##STR18## in which Brepresents ##STR19## wherein Y is hydrogen, an alkali metal cation, anammonium cation, a C₁ to C₁₈ mono-, di- or trialkylammonium cation, C₁to C₁₈ alkyl, C₂ to C₁₈ alkenyl, benzyl or benzyl substituted in thebenzene ring thereof by C₁ to C₁₂ alkyl, halo or C₁ to C₈ alkoxy, Y' ishydrogen or C₁ to C₁₈ alkyl, and Y" is hydrogen, C₁ to C₁₈ alkyl or C₄to C₁₂ N,N-dialkylaminoalkyl; R represents non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl; R⁴ represents acetamido, dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl, C₂ to C₅ acyloxy, and when one of R¹ orR² represents a carboxy or carbonyl substituent, R⁴ further representshydrogen, C₁ to C₃ alkyl, C₁ to C₄ alkoxy or halo; and R⁸ representshydrogen, C₁ to C₃ alkyl or phenyl.

In a second particular embodiment in accordance with its final productcomposition of matter aspect, the invention sought to be patentedresides in the novel 3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6')-2-R^(5') -5/6-y^(1'))-3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalidesof Formula I wherein X is 1-R⁶ -2-R⁵ -5/6-Y¹ -3-indolyl and Z is1-R^(6') -2-R^(5') -5/6-Y^(1') -3-indolyl. Preferred compounds withinthe ambit of this particular embodiment are of the formula ##STR20##wherein the indolyl moieties can be the same or different; R^(o) and R³and at least one of R¹ and R² represent hydrogen and the otherrepresents ##STR21## in which B represents ##STR22## wherein Y ishydrogen, an alkali metal cation, an ammonium cation, a C₁ to C₁₈ mono-,di- or trialkylammonium cation, C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,benzyl or benzyl substituted in the benzene ring thereof by C₁ to C₁₂alkyl, halo or C₁ to C₈ alkoxy; Y' is hydrogen or C₁ to C₁₈ alkyl; Y" ishydrogen, C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dialkylaminoalkyl; and R⁵,R^(5'), R⁶, R^(6'), Y¹ and Y^(1') each have the same respective meaningsgiven in relation to Formula I.

This invention, in a second of its composition of matter aspects,relating to intermediates, resides in the novel 2-(X-carbonyl)-3-R^(o)-4-R¹ -5-R² -6-R³ -benzoic acids which are useful as intermediates tothe final products and having the formula ##STR23## wherein R^(o), R¹,R² and R³ each represent hydrogen, or halo or when R^(o), R³ and one ofR¹ and R² are each hydrogen, the other of R¹ and R² represents amino orcarboxy; X represents a monovalent moiety selected from the class havingthe formulas ##STR24## in which R⁵ represents hydrogen, C₁ to C₃ alkylor phenyl, R⁶ represents C₄ to C₁₈ alkyl, C₂ to C₄ alkenyl, benzyl orbenzyl substituted in the benzene ring by one or two of halo or C₁ to C₃alkyl or represents hydrogen or C₁ to C₃ alkyl only when Y¹ is otherthan hydrogen and/or when one of R¹ and R² is amino or carboxy; R⁷represents hydrogen, C₁ to C₃ alkyl or phenyl; and Y¹ represents one ortwo of hydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo or nitro.

In a first particular embodiment in accordance with its composition ofmatter aspects relating to intermediates, the invention sought to bepatented resides in the novel 2-[(1-R⁶ -2-R⁵ -5/6-Y¹-3-indolyl)carbonyl]-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acids of FormulaVII wherein X is 1-R⁶ -2-R⁵ -5/6-Y¹ -3-indolyl. Preferred compoundswithin the ambit of this particular embodiment are of the formula##STR25## wherein R^(o), R¹, R², R³, R⁵, R⁶ and Y¹ each have the samerespective meanings given in relation to Formula VII.

In a second particular embodiment in accordance with its intermediatesto final products composition of matter aspect the invention sought tobe patented resides in the novel 2-[(1-R⁷ -2-pyrrolyl)carbonyl]-3-R^(o)-4-R¹ -5-R² -6-R³ -benzoic acids of Formula VII wherein X is 1-R⁷-2-pyrrolyl. Preferred compounds within the ambit of this particularembodiment are of the formula ##STR26## wherein R^(o), R¹, R², R³ and R⁷each have the same respective meanings given in relation to Formula VII.

In one of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-4-R^(o) -5-R¹ -6-R² -7-R³-phthalide according to Formula I which comprises interacting a2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acid withapproximately one molecular proportion of a 3-R⁴ -N,N-(R)₂ -aniline or a1-R^(6') -2-R^(5') -5/6-Y^(1') -indole in the presence of an anhydrideof an alkanoic acid having from 2 to 5 carbon atoms wherein R^(o), R¹,R² and R³ each represent hydrogen or halo or when R^(o), R³ and one ofR¹ and R² are each hydrogen, the other of R¹ and R² represents nitro,dialkylamino wherein alkyl is nontertiary C₁ to C₄ alkyl, or carboxy;and R, R⁴, R^(5'), R^(6') , X, Y^(1') and Z each have the samerespective meanings given in relation to Formula I.

In a second of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6-aminophthalideaccording to Formula I which comprises reducing the corresponding3-X-3-Z-5/6-nitrophthalide wherein X and Z each have the same respectivemeanings given in relation to Formula I.

In a third of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6-acetamidophthalideaccording to Formula I which comprises interacting the appropriate3-(X-carbonyl)-5/6-aminobenzoic acid with approximately one molecularproportion of a 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6') -2-R^(5')-5/6-Y^(1') -indole in the presence of at least two molecularproportions of acetic anhydride wherein R, R⁴, R^(5'), R^(6'), X, Y^(1')and Z each have the same respective meanings given in relation toFormula I.

In a fourth of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6-COOY-phthalideaccording to Formula I in which Y is C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,benzyl or benzyl substituted in the benzene ring thereof by C₁ to C₁₂alkyl, halo or C₁ to C₈ alkoxy and X and Z have the same respectivemeanings given in relation to Formula I which comprises esterifying thecorresponding 3-X-3-Z-5/6--COOH-phthalide with an appropriate compoundselected from the group consisting of dimethyl sulfate, diethyl sulfateor Y-halogen in which Y is C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, benzyl orbenzyl substituted in the benzene ring thereof by C₁ to C₁₂ alkyl, haloor C₁ to C₈ alkoxy in the presence of an alkali metal hydroxide orcarbonate.

In a fifth of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6- ##STR27## -phthalideaccording to Formula I in which Y', Y", X and Z each have the samerespective meanings given in Claim 1 which comprises amidating thecorresponding 3-X-3-Z-5/6---COOH-phthalide or appropriate carboxylicfunctional derivative thereof with the appropriate compound of theformula ##STR28## in which Y' and Y" each have the same meanings givenin relation to Formula I.

In a sixth of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalide accordingto Formula VI in which R⁵ ═R^(5'), R⁶ ═R^(6') and Y¹ ═Y^(1') whichcomprises interacting a 3-R^(o) -4-R¹ -5-R² -6-R³ -phthalic anhydridewith approximately two molecular proportions of a 1-R⁶ -2-R⁵ -5/6-Y¹-indole in the presence of an anhydride of an alkanoic acid having from2 to 5 carbon atoms wherein R^(o), R¹, R², R³, R⁵, R⁶, R^(5'), R^(6'),Y¹ and Y.sup. 1' each have the same respective meanings given inrelation to Formula VI.

In a seventh of its process aspects, the invention sought to be patentedresides in the process for preparing a 2-(X-carbonyl)-3-R^(o) -4-R¹-5-R² -6-R³ -benzoic acid according to Formula VII which comprisesinteracting a 3-R^(o) -4-R¹ -5-R² -6-R³ -phthalic anhydride withapproximately one molecular proportion of a 1-R⁶ -2-R⁵ -5/6-Y¹ -indoleor a 1-R⁷ -pyrrole in the presence of a Lewis acid wherein R^(o), R¹, R²and R³ each represent hydrogen or halo or when R^(o), R³ and one of R¹and R² are each hydrogen, the other of R¹ and R² represents carboxy andR⁵, R⁶, R⁷, X and Y¹ each have the same respective meanings given inrelation to Formula VII.

In an eighth of its process aspects, the invention sought to be patentedresides in the process for preparing a 2-(X-carbonyl)-5/6-amino-benzoicacid according to Formula VII which comprises reducing the corresponding2-(X-carbonyl)-5/6-nitrobenzoic acid wherein X has the same meaninggiven in relation to Formula VII.

In an article-of-manufacture aspect, the invention sought to be patentedresides in a pressure-sensitive carbonless duplicating system, thermalmarking system or hectographic copy system containing as a color-formingsubstance a 3-X-3-Z-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalide according toFormula I wherein R^(o), R¹, R², R³, X and Z have the same respectivemeanings given in relation to Formula I.

A particular embodiment sought to be patented resides in apressure-sensitive transfer sheet, adapted for use with a receivingsheet having an electron accepting layer, comprising a support sheetcoated on one side with a layer of pressure-rupturable microcapsules,said microcapsules containing a liquid solution of a color formingsubstance comprising at least one compound having Formula I.

Another particular embodiment sought to be patented resides in a heatresponsive record material comprising a support sheet coated on one sidewith a layer containing a mixture comprising at least one color-formingcompound having Formula I and an acidic developer arranged such thatapplication of heat will produce a mark-forming reaction between thecolor-forming compound and the acidic developer.

Preferred articles within the ambit of the particular embodimentsabove-described are those wherein the color-forming component comprisesa 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-[-(1-R⁵ -2-R⁶ -5/6-Y¹)-3-indolyl]-4-R^(o)-5-R¹ -6-R² -7-R³ -phthalide wherein R, R^(o), R¹, R², R³, R⁴, R⁵, andR⁶ and Y¹ have the same respective meanings given in relation to FormulaIII or a 3-[(1-R⁵ -2-R⁶ -5/6-Y¹)-3-indolyl]-3-[(1-R^(5') -2-R^(6')-5/6-Y^(1'))- 3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalide whereinR^(o), R¹, R², R³, R⁵, R⁶, R^(5'), R^(6'), Y¹ and Y^(1') and have thesame respective meanings given in relation to Formula VI.

A further particular embodiment sought to be patented resides in ahectographic or spirit reproducing copying system comprising a transfersheet coated on one side with a layer containing a color-formingsubstance comprising a compound according to Formula I wherein R^(o), R³and one of R¹ and R² are each hydrogen, the other of R¹ and R²represents ##STR29## wherein Y is hydrogen, an alkali metal cation, anammonium cation or a C₁ to C₁₈ mono-, di- or trialkylammonium cation.

As used herein the term "halo" includes chloro, fluoro, bromo and iodo.Chloro is the preferred halo substituent because of the relatively lowcost and ease of preparation of the required chloro-substitutedintermediates and because the other halogens offer no particularadvantages over chloro. However the other above-named halo substituentsare also satisfactory.

The terms "C₁ to C₄ alkoxy", "C₂ to C₅ acyloxy" and "dialkylamino inwhich alkyl is non-tertiary C₁ to C₄ alkyl" denote saturated, acyclicgroups which may be straight or branched as exemplified by methoxy,ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy,acetyloxy, propionyloxy, dimethylamino, diethylamino, ethylmethylamino,dipropylamino, dibutylamino, isobutylmethylamino, and the like.

As used herein the terms "C₁ to C₃ alkyl", "C₁ to C₁₂ alkyl" and "C₁ toC₁₈ alkyl" denote saturated monovalent straight or branched aliphatichydrocarbon radicals including methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, 1-methylbutyl, 3-methylbutyl, hexyl,isohexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl,3-ethylheptyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,1,3,5-trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butyl-hexyl,2-propylnonyl, 2-butyloctyl, 2-pentylnonyl, 1,2-dimethylhexadecyl, andthe like.

As used herein the term "alkali metal cation" includes lithium, sodiumand potassium cations.

The term "C₁ to C₁₈ alkylammonium cation" includes ammonium cationssubstituted by from 1 to 3 alkyl groups as above described. The alkylgroups can be the same or different provided the ammonium cationcontains no more than 18 carbon atoms. As examples there can be namedmethylammonium, t-butylammonium, t-octylammonium, n-dodecylammonium,n-octadecylammonium, di-n-butylammonium, di-n-nonylammonium,isopropyl-n-butylammonium, dimethyl-n-butylammonium, triethylammonium,N-ethyl-N,N-diisopropylammonium, tributylammonium,di-n-butyl-n-octylammonium and the like.

The terms "C₁ to C₈ " alkoxy and "C₁ to C₁₈ alkoxy" includes saturated,acyclic, straight or branch-chained groups such as methoxy, ethoxy,propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy,n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy,n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy,n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy,1-methylpentyloxy, 2,2-dimethylbutyloxy, 2-methylhexyloxy,1,4-dimethylpentyloxy, 3-ethylpentyloxy, 2-methylheptyloxy,1-ethylhexyloxy, 2-propylpentyloxy, 2-methyl-3-ethylpentyloxy,1,3,5-trimethylhexyloxy, 1,5-dimethyl-4-ethylhexyloxy,5-methyl-2-butylhexyloxy, 2-propylnonyloxy, 2-butyloctyloxy,1,1-dimethylundecyloxy, 2-pentylnonyloxy, B 1,2-dimethyltetradecyloxy,1,1-dimethylpentadecyloxy and the like.

The term "C₄ to C₁₂ N, N-dialkylaminoalkyl" includes branched andstraight chain alkyl groups which can be the same or different providedthat the total number of carbon atoms is not less than four nor morethan twelve. As examples there can be named 2-dimethylaminoethyl,diethylaminomethyl, 3-dimethylaminopropyl, 1-dimethylamino-2-propyl,3-diethylaminopropyl, 1-diethylamino-2-propyl, 2-dipropylaminoethyl,2-di-i-propylaminoethyl, 3-dipropylaminopropyl, 3-dimethylaminopropyl,4-diethylamino-n-butyl, 3-dibutylaminopropyl, 4-dimethylamino-n-butyl,5-diethylaminopentyl, 5-dipropylaminopentyl, 6-dimethylamino-n-hexyl,6-diethylamino-6-ethylhexyl, 4-dibutylamino-n-butyl,8-dimethylamino-n-octyl, 8-diethylamino-n-octyl,10-dimethylamino-n-decyl, 5-dipropylamino-2-pentyl and the like.

As used herein, the term "C₂ to C₁₈ alkenyl" means a monovalentaliphatic radical possessing a single double bond, for example, ethenyl(or vinyl), 2-propenyl (or allyl), 1-methylethenyl (or isopropenyl),2-methyl-2-propenyl, 2-methyl-1-propenyl, 2-butenyl, 3-butenyl,1-pentenyl, 2-pentenyl, 3-methyl-2-butenyl, 2-methyl-1-butenyl(isoamylenyl), 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl,2-heptenyl, 1-octenyl, 1-hexadecenyl, 9-octadecenyl, 9-decenyl,1-methyl-4-butenyl, 4-pentenyl, 1-ethyl-1-propenyl, 1-ethyl-3-propenyl,10-undecenyl and the like.

Anhydrides of alkanoic acids of two to five carbon atoms include aceticanhydride, propionic anhydride, butyric anhydride, isobutyric anhydride,valeric anhydride, isovaleric anhydride, α-methylbutyric anhydride,pivalic anhydride and the like. Acetic anhydride is preferred because ofits low cost and high reactivity, however the other above-namedanhydrides are also satisfactory.

The novel compounds of Formula I hereinabove are essentially colorlessin the depicted form. When contacted with an acidic medium, for examplesilica gel or one of the types ordinarily employed in pressure-sensitivecarbonless duplicating systems such as silton clay or phenolic resinsthe compounds of Formula I develop an orange-red through green to ablackish-purple colored image of good to excellent tinctorial strength,and possessing excellent light stability, resistance to sublimation andxerographic copiability. The compounds are thus highly suitable for useas colorless precursors, that is color-forming substances inpressure-sensitive carbonless duplicating systems. The darker violetsand bluish-black colors can be used alone as color formers to produceimages which are readily copiable, whereas the reds, greens and bluecolors can be used as toners in admixture with other color formers toproduce images of a neutral shade which desirably are readily copiableby xerographic means. Moreover, the compounds of Formula I, inparticular those wherein one of R¹ and R² represents ##STR30## in whichB represents ##STR31## wherein Y is C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,benzyl or benzyl substituted in the benzene ring thereof by C₁ to C₁₂alkyl, halo or C₁ to C₈ alkoxy; Y' is hydrogen or C₁ to C₁₈ alkyl; Y" ishydrogen, C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dialkylaminoalkyl haveenhanced solubility in common and inexpensive organic solvents such asodorless mineral spirits, kerosene, vegetable oils and the like; andthose wherein one of R¹ and R² is an alkali-metal cation, an ammoniumcation or a C₁ to C₁₈ mono-, di- or trialkylammonium cation salt of thecarboxy group are soluble in water and lower-alkanols thereby avoidingthe need for more expensive, specialized solvents such aspolyhalogenated or alkylated biphenyls which have ordinarily been usedto prepare microencapsulated solutions of the color formers of the priorart.

The compounds of this invention may be incorporated in any of thecommercially accepted systems known in the carbonless duplicating art. Atypical technique for such application is as follows. Solutionscontaining one or more colorless precursor compounds of Formula I,optionally in admixture with other color formers, in suitable solventsare microencapsulated by well-known procedures for example as describedin U.S. Pat. No. 3,649,649. The microcapsules are coated on the reverseside of a transfer sheet with the aid of a suitable binder and thecoated transfer sheet is then assembled in a manifold with themicrocapsule coated side in contact with a receiving sheet coated withan electron accepting substance, for example, silton clay or a phenolicresin. Application of pressure to the manifold such as that exerted by astylus, typewriter or other form of writing or printing causes thecapsules on the reverse side to rupture. The solution of the colorformer released from the ruptured microcapsules flows to the receivingsheet and on contact with the acidic medium thereon forms orange-red toviolet-black colored images of good tinctorial strength. It is, ofcourse, obvious that variants of this mode of application can beutilized. For example, the receiving sheet in a manifold canalternatively be coated with the subject compounds and the acidicdeveloping agent can be contained in microcapsules applied to thereverse side of the top sheet in the manifold; or the receiving sheetcan be coated with a mixture containing both the acidic developing agentand the microencapsulated color former.

It has also been found that when the compounds of Formula I areintimately mixed with an acidic developer of the type generally employedin thermal papers such as described in U.S. Pat. No. 3,539,375, that is,papers which produce a colored image when contacted with a heated stylusor heated type, for example, bisphenol A, heating of the mixtureproduces a colored image of varying shades from orange-red toviolet-black depending on the particular compound of the inventionemployed. The ability of the compounds of Formula I to form a deep colorwhen heated in admixture with an acidic developer such as bisphenol A,makes them useful in thermal paper marking systems, either where anoriginal or a duplicate copy is prepared by contacting the thermal paperwith a heated stylus or heated type in any of the methods generallyknown in the art.

The compounds of this invention which are soluble in water andlower-alkanols may be incorporated in any of the commercial hectographicor spirit-reproducing copying systems such as described in British Pat.No. 1,427,318 published Mar. 10, 1976. In such systems a transfer sheetcoated on one side with a layer containing one or more water- or loweralkanol-soluble color formers of Formula I is placed with its coatedsurface against one surface of a master paper which is then typed,written or marked on, causing transfer of the coating as a substantiallycolorless reverse image to the master paper at the points where thetransfer sheet and master paper have been pressed together. The masterpaper is then brought into contact with a succession of sheets of papermoistened with a suitable spirit-reproducing fluid such as ethanol. Thefluid dissolves a part of the color former and transfers it to eachpaper sheet where it combines with an electron-accepting substance, togive a orangish-red to violet-black colored image which duplicates theoriginal typing or writing on the master paper.

The best mode contemplated by the inventors of carrying out thisinvention will now be described so as to enable any person skilled inthe art to which it pertains to make and use the same.

In accordance with one of the process aspects of this invention the3-X-3-Z-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides of Formula I whereinR^(o), R¹, R² and R³ each represent hydrogen or halo or when R^(o), R³and one of R¹ and R² are each hydrogen and the other represents nitro,dialkylamino or carboxy are obtained by interacting approximately anequimolar quantity of the appropriate 2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R²-6-R³ -benzoic acid with the appropriate 3-R⁴ -N,N-(R)₂ -aniline or a1-R^(6') -2-R^(5') -5/6-Y^(1') -indole. The reaction is convenientlycarried out in the presence of an anhydride of an alkanoic acid havingfrom 2 to 5 carbon atoms, for example, acetic anhydride at a temperaturein the range of 10° to 140° C. for from approximately thirty minutes toeighteen hours. The 3-X-3-Z-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalide thusobtained can be isolated by filtration if it is insoluble in thereaction medium or by dilution of the reaction medium with a misciblesolvent in which the product is insoluble, for example, a loweralkanolor low molecular weight hydrocarbon, for example, isopropyl alcohol orhexane to effect precipitation of the phthalide. Alternatively, thereaction mixture can be poured into an aqueous base or an aqueous baseadded to the reaction mixture, for example, dilute ammonium hydroxide,sodium hydroxide or sodium carbonate and the phthalide extracted with anorganic solvent, for example, benzene or toluene followed by evaporationof the organic solvent leaving the product as a residue. The phthalideonce isolated can be purified by conventional means such as triturationor recrystallization from a suitable solvent. In a second alternativemethod, the reaction mixture can be added to an aqueous acid, forexample, dilute hydrochloric acid and the pH adjusted by the addition ofa dilute alkali, for example, dilute aqueous ammonium hydroxide or analkaline salt, for example, sodium acetate and the product filtered orextracted as described above.

The 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-X-4-R^(o) -5-R¹ -6-R² -7-R³ phthalidesof Formula II wherein R⁴ is acyloxy can be prepared from thecorresponding 3-acyloxy-N,N(R)₂ aniline in the manner described above.However, these compounds are conveniently prepared by interacting theappropriate 3-hydroxy-N,N(R)₂ aniline with the appropriate2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ benzoic acid in the presence ofan anhydride of an alkanoic acid as described above under whichconditions the hydroxy group is simultaneously acylated during thecourse of the reaction.

The 3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides of FormulaVI in which the indole moieties are the same can be prepared byinteracting trimellitic anhydride with approximately two molecularproportions of the appropriate 1-R⁶ -2-R⁵ -5/6-Y¹ -indole. The reactionis conveniently carried out in the anhydride of an alkanoic acid havingfrom two to five carbon atoms, for example acetic anhydride at atemperature in the range of 10° to 140° C., but more desirably, at atemperature in the range of 75° to 140° C. to obtain the desired3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-5/6-carboxyphthalide. The phthalides areisolated in a manner similar to that indicated in the first mode ofsynthesis described above.

In accordance with a further process aspect of the present invention the3-X-3-Z-5/6-aminophthalides of Formula I can be prepared by reducing thecorresponding 3-X-3-Z-5/6-nitrophthalide. The reduction is convenientlycarried out in an acidic medium, for example, hydrochloric acid using ametal salt reducing agent, for example, stannous chloride at atemperature in the range of 0° to 80° C., but more desirably, at atemperature in the range of 50°-80° C. The desired phthalide iscollected by filtration and purified by conventional means for examplerecrystallization from a suitable solvent after an aqueous alkaliextraction.

In accordance with a fourth of the process aspects of this invention,the 3-X-3-Z-5/6-acetamidophthalide according to Formula I can beconveniently obtained by interacting the appropriate3-(X-carbonyl)-5/6-aminobenzoic acid with approximately an equimolarquantity of an appropriate 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6')-2-R^(5') -5/6-Y^(1') -indole in the presence of at least two molecularproportions of acetic anhydride. The product is isolated by adding waterand dilute alkali to the reaction mixture and the product extracted withan organic solvent, for example, benzene or toluene followed byevaporation of the organic solvent leaving the phthalide as acrystalline material.

The 3-X-3-Z-5/6-COOY-phthalides of Formula I in which Y is a C₁ to C₁₈alkyl, a C₂ to C₁₈ alkenyl, a benzyl or a benzyl substituted in thebenzene ring thereof by C₁ to C₁₂ alkyl, halo or C₁ to C₈ alkoxy areobtained by interacting a 3-X-3-Z-5/6-COOH-phthalide with an appropriatealkylating agent, for example, dimethyl sulfate, diethyl sulfate, ethyliodide, butyl bromide, allyl chloride, octyl bromide, hexadecyl bromideor benzyl bromide in an inert diluent, for example, acetone,N,N-dimethylformamide or hexamethylphosphoramide in the presence of analkali metal salt, for example, sodium hydroxide, sodium carbonate,potassium hydroxide or potassium carbonate. The reaction is convenientlycarried out at a temperature in the range of 10° to 100° C. forapproximately one to three hours. The 3-X-3-Z-5/6-COOY-phthalide thusobtained is isolated by adding the reaction mixture to water withsubsequent extraction into and subsequent isolation from an aromaticsolvent, for example, benzene or toluene. The organic layer isseparated, dried over a suitable drying agent, followed by evaporationof the organic solvent leaving the phthalide as a residue. The productonce isolated can be purified by conventional means such as triturationor recrystallization from a suitable solvent.

In accordance with another process aspect of this invention the3-X-3-Z-5/6-CONY'Y"-phthalides of Formula I are obtained by amidatingthe corresponding 3-X-3-Z-5/6-COOH-phthalide or the appropriatecorresponding 3-X-3-Z-5/6-COOY-phthalide with the appropriate Y'Y"NHamine, for example, 3-(di-n-butylamino)propylamine. The reaction isconveniently carried out optionally in the presence of an inert diluentor in the absence of an inert diluent at a temperature in the range of90° to 150° C. for approximately five hours. The phthalide thus obtainedcan be isolated by adding the reaction mixture to water and the prouctextracted with an organic solvent, for example, benzene or toluene. Theorganic layer is separated and evaporated or distilled in vacuum toleave the product as a residue or oil.

The 3-X-3-Z-5/6-COOY-phthalides wherein the Y is an alkali metal cation,an ammonium cation or a mono-, di- or trialkylammonium cation areobtained by interacting the appropriate 3-X-3-Z-5/6-COOH-phthalide withapproximately an equimolar quantity of an appropriate alkali metal salt,for example, sodium hydroxide, potassium hydroxide or lithium hydroxide,ammonium hydroxide or an amine, for example,1,1,3,3-tetramethylbutylamine. The reaction is conveniently carried outin an inert diluent, for example, acetone at a temperature in the rangeof 10° to 50° C. for approximately five minutes to one hour. Thephthalide thus obtained is isolated by dilution of the reaction mediumwith a miscible solvent in which the product is insoluble, for example,low molecular weight hydrocarbons such as hexane in order to effectprecipitation of the product. The phthalide once isolated can bepurified by conventional means such as trituration or recrystallizationfrom a suitable solvent.

Both the known and the novel 2-X-carbonyl-3-R^(o) -4-R¹ -5-R² -6-R³-benzoic acids of Formula VII are prepared in similar fashion, byinteracting a 3-R^(o) -4-R¹ -5-R² -6-R³ -phthalic anhydride with a 1-R⁶-2-R⁵ -5/6-Y¹ -indole, a 1-R⁷ -pyrrole, or a 9-R⁸ -carbazole whereinR^(o), R¹, R², R³, R⁵, R⁶, R⁷, R⁸ and Y¹ each have the same meaningsgiven in relation to Formula I usually in the presence of a Lewis acid,for example, aluminum chloride or zinc chloride, and with a diluent suchas benzene, toluene, xylene, chlorobenzene, 1,2-dichloroethane oro-dichlorobenzene at a temperature of about 0° to 150° C. The reactionis conveniently carried out in toluene in the presence of aluminumchloride at about 0° to 25° C. Alternatively, the more reactive indolescan be interacted in the absence of a Lewis acid by simply heating thereactants together in an inert solvent at about 80° to 150° C. The2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acids in which Lewisacids are used in their preparation are isolated by adding water to thereaction mixture or the reaction mixture to water or dilute mineralacid, for example, hydrochloric acid and subsequently separating theorganic layer. The product is extracted from the organic layer with adilute aqueous alkali solution and precipitated by the addition of amineral acid, for example, hydrochloric acid. The benzoic acid iscollected by filtration and may be purified by conventional means but isgenerally dried and used as is. Alternatively, in the case where themore reactive indoles are utilized, it is preferable not to use a Lewisacid and the 2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acids areobtained by cooling the reaction mixture to ambient temperature andcollecting the product by filtration. The product once isolated can bepurified by conventional means but preferably the benzoic acid is driedand used as is.

In accordance with one of the process aspects of this invention, the2-(X-carbonyl)-5/6-aminobenzoic acids of Formula VII are obtained byreducing the corresponding 2-(X-carbonyl)-5/6-nitrobenzoic acid. Thereduction is conveniently carried out in an acidic medium, for example,hydrochloric acid using a metal salt reducing agent, for example,stannous chloride at a temperature in the range of 0° to 80° C., butpreferably at a temperature in the range of 50°-80° C. The desiredbenzoic acid is collected by filtration and purified if desired byconventional means but perferably it is dried and used as is.

It will, of course, be appreciated that reaction of an unsymmetricallysubstituted phthalic anhydride with an indole, pyrrole or carbazole canproduce isomers or a mixture of isomers of 2-(heteroarylcarbonyl)benzoicacids. For example, reaction of a 4-substituted phthalic anhydride withan indole, pyrrole or carbazole can produce either a 4- or 5-substituted2-(heteroarylcarbonyl)benzoic acid or a mixture thereof. Similarily a3-substituted phthalic anhydride can produce either a 3- or a6-substituted 2-(heteroarylcarbonyl)benzoic acid or a mixture of these.These mixtures of isomeric 2-(heteroarylcarbonyl)benzoic acids can beseparated by conventional means such as fractional crystallization orchromatography. Alternatively, the isomeric mixtures can be reacteddirectly with appropriate 3-R⁴ -N,N-(R)₂ -anilines or 1-R^(6') -2-R^(5')-5/6-Y^(1') -indoles to produce isomeric mixtures of phthalides ofFormula I. Thus, reaction of a mixture of 4- and 5-substituted2-(heteroarylcarbonyl)benzoic acids with a 3-R⁴ -N,N-(R)hd 2-aniline ora 1-R^(6') -2-R^(5') -5/6-Y^(1') -indole will produce a mixture of 5-and 6-substituted phthalides. The mixtures of phthalides can, ifdesired, be separated by conventional means or simply and preferablyused as mixtures in the practice of this invention. Throughout thisapplication where the possibility of different isomeric products beingformed is present, the nomenclature 4/5, 5/6 and so forth is adoptedmeaning the product obtained or claimed is a mixture of the isomers.

Indole, the substituted indoles, pyrrole, the substituted pyrroles,carbazole and the substituted carbazoles required as intermediates forthe preparation of the carbonylbenzoic acid intermediates of FormulasVII, VIII and IX and for the final products of Formulas I, II, III, IV,V and VI form an old and well-known class of compounds which are readilyobtained by conventional procedures well known in the art. The followingcompounds are exemplary of indoles, pyrroles and carbazoles useful inthe practice of this invention.

Indole,

1-Methylindole,

2-Methylindole,

1,2-Dimethylindole,

1-Ethyl-2-methylindole,

2-Phenylindole,

1-Propyl-2-methylindole,

1-Benzyl-2-methylindole,

1-Butyl-2-methylindole,

1-Octyl-2-methylindole,

2-Ethyl-5-methylindole,

1-Benzyl-5-fluoroindole,

1-Methyl-6-nitroindole,

5-Methoxy-1-butylindole,

1-Allyl-2-methylindole,

1,2-Dimethyl-6-nitroindole,

1-(4-Chlorobenzyl)-2-methyl-5-nitroindole,

2-Ethylindole,

2-Ethyl-1-methylindole,

1-Isopropylindole,

2-Isopropylindole,

1-Methyl-5-bromo-6-nitroindole,

2,5,6-Trimethylindole,

1-Isobutyl-2-methylindole,

6-Bromo-2-methylindole,

1-Hexylindole,

1-(2,5-Dimethylbenzyl)-2-methylindole,

2-Propylindole,

6-Chloro-2-phenylindole,

1-(2-Ethylhexyl)-2-methylindole,

1-(2,6-Dichlorobenzyl)-2-methylindole,

1-Vinyl-2-methylindole,

2-Ethyl-6-methylindole,

6-Fluoro-1-benzylindole,

1-(4-Bromobenzyl)-2-isopropylindole,

1-(3-Chlorobenzyl)-2-ethylindole,

5-Chloro-1-benzylindole,

1-(2-Fluorobenzyl)-2-methylindole,

5-Iodo-1-(1-methylhexyl)indole,

5,6-Dimethoxyindole,

1-(2-Methylbenzyl)-2-methylindole,

5,6-Dichloro-2-phenylindole,

1-Isoamylindole,

1-[3-(2-Methyl)-1-propenyl]-2-methoxyindole,

Pyrrole,

N-Methylpyrrole,

N-Ethylpyrrole,

N-Propylpyrrole,

N-Isopropylpyrrole,

N-Phenylpyrrole,

Carbazole,

9-Methylcarbazole,

9-Ethylcarbazole,

9-Propylcarbazole,

9-Isopropylcarbazole, and

9-Phenylcarbazole.

The 3-R⁴ -N,N-(R)₂ -anilines, which are required for interaction withthe 2-(X-carbonyl)-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acids of FromulaVII to obtain the 3-X-3-[2-R⁴ -4-N(R)₂ -phenyl]-4-R^(o) -5-R¹ -6-R²-7-R³ -phthalides of Formula II form an old and well-known class ofcompounds readily obtained by conventional procedures well known in theart. The following list of anilines exemplifies compounds which fallwithin the ambit of the formula Z-H or are useful in the practice of thestep in the processes of this invention for producing the aforesaidphthalides of Formula II.

N,N,N',N'-Tetramethyl-m-phenylenediamine,

N,N-Dibutylaniline,

N,N-Diethyl-3-ethoxyaniline,

N,N-Diethyl-m-anisidine,

N,N-Dimethylaniline,

N-Benzyl-N-ethylaniline,

N,N-Diethyl-m-toluidine,

N,N-Diethylaniline,

N-Ethyl-N-methylaniline,

N-Benzyl-N-methylaniline,

N-Benzyl-N-propylaniline,

N,N-Dimethyl-3-bromoaniline,

N,N,N',N'-Tetraisopropyl-m-phenylenediamine,

N,N-Dibutyl-3-fluoroaniline,

N,N-Diethyl-2-methoxy-3-chloroaniline,

N-Benzyl-N-methyl-3-ethylaniline,

N,N,N',N'-Tetra-sec-butyl-m-phenylenediamine,

N-Benzyl-N-butyl-3-iodoaniline,

N,N-Diisopropyl-3-chloroaniline,

N-Benzyl-N-sec-butylaniline,

N,N-Diethyl-3-hydroxyaniline

N,N-Dimethyl-3-hydroxyaniline

N,N-Di-sec-butylaniline,

N,N-Diethyl-3-isopropylaniline,

N,N-Diisobutylaniline,

N,N-Diethyl-2-propoxyaniline,

N,N-Dipropylaniline,

N-Isopropyl-N-methylaniline,

N-Methyl-N-propylaniline,

N,N,N',N'-Tetrabutyl-m-phenylenediamine,

N,N-Dipropyl-o-anisidine,

N-Isobutyl-N-ethylaniline,

N,N,N',N'-Tetraethyl-m-phenylenediamine,

N-Propyl-N-ethylaniline,

N,N-Diethyl-2-ethoxyaniline,

N-Benzyl-N-sec-butyl-2-propoxyaniline, and

N,N-Dimethyl-m-toludine.

N,N-Dimethyl-3-acetyloxyaniline

N,N-Diethyl-3-acetyloxyaniline

The molecular structures of the compounds of this invention wereassigned on the basis of the modes of synthesis, elemental analysis andstudy of their infrared, nuclear magnetic resonance, and mass spectra.

The following examples will further illustrate the invention without,however, limiting it thereto.

EXAMPLE 1

A. To a stirred suspension of 22.5 g (0.15 mole) of phthalic anhydrideand 61.0 g (0.30 mole) of 77.5 percent active 1-ethyl-2-methylindole in120 ml of ethylene dichloride chilled to 0° to 5° C. by means of an icebath, there was added in small portions 32.0 g (0.24 mole) of aluminumchloride. The mixture was maintained at 0°-5° C. for an additional 15minutes, allowed to warm to room temperature and stirred overnight.Then, 240 ml of water was added to the reaction mixture and the ethylenedichloride layer was separated from the acidic aqueous layer. Theorganic layer was extracted with 600 ml of 3.5 percent aqueous sodiumhydroxide. The alkaline extract was acidified with dilute hydrochloricacid and the separated solid collected, washed with water and dried toobtain 24.0 g of 2-[(1-ethyl-2-methyl-3-indolyl)carbonzyl]benzoic acid(Formula VIII: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃), aslightly pink solid having a melting point of 184°-185° C.

B. A mixture of 12.28 g (0.04 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, 10.7 g (0.043 mole) of 90 percent activeN,N,N',N'-tetraethyl-m-phenylenediamine and 6.0 ml of acetic anhydridewas stirred at room temperature for seventeen hours. The reactionmixture was diluted with 26.0 ml of ethanol, stirred and filtered. Theseparated solid was washed with diethylether and dried to yield 11.8 gof3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁶ ═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂; R⁵ ═CH₃), a white crystalline material which melted at 139°-140° C.The infrared spectrum showed a significant band at 1760 cm⁻¹ (C═O; s)and the nuclear magnetic resonance spectrum was in accord with thestructure. A solution of this product in benzene developed a deepblue-black color when spotted on silica gel.

C. In a procedure similar to that described above in part B of thisexample, 12.28 g (0.04 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, 8.57 g (0.05 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 6.0 ml of acetic anhydridewere interacted with stirring at room temperature overnight. Thereaction mixture was then diluted with 13.0 ml of ethanol and theprecipitate which separated was filtered and washed with 6.0 ml ofethanol. The filter cake was then reslurried in 30 ml of methanol,filtered and washed successively with methanol and diethylether. Thematerial was dried in vacuo to obtain 15.8 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶═CH₂ CH₃), a white crystalline solid which melted at 218°-222° C. Theinfrared spectrum was consistent with the structure. A benzene solutionof the above product developed an intense grape-red color when streakedon a phenolic resin coated paper.

EXAMPLE 2

A. To a stirred suspension of 9.66 g (0.017 mole) of tetrachlorophthalicanhydride and 13.5 g (0.034 mole) of 80 percent active1-ethyl-2-methylindole in 30 ml of benzene maintained at 0°-5° C. bymeans of an ice bath, 10.6 g (0.079 mole) of aluminum chloride was addedin small increments. The reaction mixture was then maintained at 0° to5° C. for an additional twenty minutes, allowed to warm to roomtemperature and stirred overnight. The mixture was transferred to abeaker and triturated successively with hexane, 10 percent hydrochloricacid, and lastly with 5 percent aqueous sodium hydroxide which had beenheated to 70° C. The residual oil was filtered, acidified with diluteshydrochloric acid and allowed to stand overnight. On standing, the oilgave way to a solid which was collected by filtration, washed with waterand dried to yield 6.8 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acid(Formula VIII: R^(o) ═R¹ ═R² ═R³ ═Cl; R⁵ ═CH₃ ; R⁶ ═CH₃ CH₂ ; Y¹ ═H), anoff white solid melting at 214°-216° C. Analysis by mass spectrum showedm/e peaks at 443 (M⁺, Cl═35) and 398 (M⁺ --COOH).

B. A stirred mixture of 8.86 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared as described in part A above, 4.0 g ofN,N,N',N'-tetramethyl-m-phenylenediamine, and 10.0 ml of aceticanhydride was heated at reflux for a period of three hours. The reactionwas then allowed to cool to room temperature, and the tan precipitatewhich formed was filtered and washed with isopropanol. The material thusobtained was dissolved in 500 ml of benzene and the resulting solutionextracted with 70 ml of 10 percent aqueous sodium hydroxide. The benzenesolution was filtered and evaporated to dryness at ambient temperatureyielding 1.5 g of3-[2,4-bis(dimethylamino)-phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═CH₂CH₃ ; Y¹ ═H), a white solid which melted with decomposition at 227°-229°C. A significant infrared maximum occurred at 1770 cm⁻¹ (C═O; s). Thenuclear magnetic resonance spectrum was in complete agreement with theassigned structure. A benzene solution of this product spotted on silicagel developed an intense purple color.

EXAMPLE 3

A. A solution of 67.2 g (0.4 mole) of 4-nitrophthalic anhydride and 63.0g (0.32 mole) of 80.6 percent active 1-ethyl-2-methylindole in 50 ml ofethylene dichloride was heated at reflux for two hours. The reactionmixture was then allowed to cool to room temperature. The yellowprecipitate which separated was collected by filtration, washed withfresh ethylene dichloride and dried to obtain 64.5 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-nitrobenzoic acid (FormulaVIII: R^(o) ═R² ═R³ ═Y¹ ═H; R¹ ═NO₂ ; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃) having amelting point of 203°-204° C.

B. A mixture of 3.68 g (0.01 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-nitrobenzoic acid, preparedas described in part A above, and 2.0 g (0.012 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine in 10.0 ml of acetic anhydridewas heated at 90° C. for one hour and then allowed to cool to 25° C. Thesolid which separated was collected by filtration, washed withdiethylether and dried to obtain 3.8 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide(Formula III: R^(o) ═R¹ ═R³ ═Y¹ ═H; R² ═NO₂ ; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ;R⁶ ═CH₂ CH₃) as an orange solid which melted over the range 185°-187° C.The nuclear magnetic resonance spectrum was in accord with the assignedstructure. A benzene solution of this product developed a black-purplecolor when spotted on silica gel.

C. A solution of 25.0 g (0.054 mole) of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide,prepared as described in part B above, in 285 ml of concentratedhydrochloric acid was heated to 60° C. at which temperature 31.25 g(0.142 mole) of stannous chloride dihydrate was added at such a rate asto maintain the temperature of 60° C. After the addition was complete,the solution was heated to 70° C. and held there for a period of onehour and then allowed to cool to 25° C. The green-colored solid whichseparated was collected by filtration and was slurried in five percentaqueous sodium hydroxide solution. The resulting suspension wasextracted with 500 ml of toluene at room temperature and the tolueneextract was filtered, decolorized, and dried over sodium sulfate. Onstanding, a cream solid separated from the toluene solution. The solidwas filtered off and dried to obtain 2.9 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-aminophthalide(Formula III: R^(o) ═R¹ ═R³ ═Y¹ ═H; R² ═NH₂ ; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ;R⁶ ═CH₂ CH₃) having a melting point of 206°-209° C. Infrared analysisshowed a maximum at 1727 cm⁻¹ (C═O; s). The nuclear magnetic resonancespectrum was concordant with the assigned structure. A toluene solutionof the above compound developed an intense grape-black color whenspotted on a paper coated with phenolic resin.

D. To a solution of 7.04 g (0.02 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-nitrobenzoic acid, preparedas described in part A of this example, in 70 ml of concentratedhydrochloric acid, there was added 13.5 g (0.06 mole) of stannouschloride dihydrate at such a rate as to allow the reaction to exothermto 55° C. The temperature was maintained at 55° C. for an additionalone-half hour. The reaction was then cooled to room temperature and thepH adjusted to six by the addition of 10 percent aqueous sodiumhydroxide solution. The red precipitate thus formed was filtered off andextracted into acetone. The acetone solution was evaporated and thepaste-like residue was slurried in diethylether and then the solid wascollected by filtration to obtain 3.5 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-aminobenzoic acid (FormulaVIII: R³ ═R² ═R^(o) ═Y¹ ═H; R¹ ═NH₂ ; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃), a redsolid which melted at 187°-189° C.

E. A mixture of 3.22 g (0.01 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-aminobenzoic acid, 118 g(0.01 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine in 10.0 ml ofacetic anhydride was heated to 50° C. for one-half hour. After coolingto ambient temperature, 50 ml of water was added and the reactionmixture was filtered. The filtrate was rendered alkaline with diluteaqueous sodium hydroxide in the presence of 100 ml of toluene. Thetoluene layer was separated, dried and evaporated to obtain as tancrystals3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-acetamidophthalide(Formula III: R^(o) ═R¹ ═R³ ═Y¹ ═H; R² ═NHCOCH₃ ; R═R⁵ ═CH₃ ; R⁴═N(CH₃)₂ ; R⁶ ═CH₂ CH₃) having a melting point of 204°-206° C. Infraredanalyses showed maxima at 1733 cm⁻¹ (C═O; s) and 1695 cm⁻¹ (C═O; s).Nuclear magnetic resonance analysis was consistent with the structure.An acetone solution of the above compound developed an intense grapecolor when spotted on silica gel.

EXAMPLE 4

A. Following the procedure described in part A of Example 1, 7.4 g (0.05mole) of phthalic anhydride, 16.0 g (0.07 mole) of 79 percent active1-n-butyl-2-methylindole and 13.3 g (0.01 mole) of aluminum chloridewere interacted in 50 ml of benzene to obtain2[(1-n-butyl-2-methyl-3-indolyl)carbonyl]benzoic acid (Formula VIII:R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═(CH₂)₃ CH₃) a pale pink solidmelting over the range 88°-92° C. The nuclear magnetic resonancespectrum was consistent with the structure. Infrared maxima wererecorded at 1720 cm⁻¹ (C═O; s) and 1700 cm³¹ 1 (C═O; s).

B. A mixture of 3.35 g (0.01 mole) of2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, 1.80 g (0.011 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and five ml of acetic anhydridewas stirred at ambient temperature for a period of approximately 18hours. The reaction mixture was then poured into a mixture of 40 ml ofwater, 40 ml of ligroin and 20 ml of 10 percent aqueous sodiumhydroxide. The ligroin layer was separated and the white crystals whichseparated from the solution on standing, were collected by filtrationand dried to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-butyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶═(CH₂)₃ CH₃) which melted at 165°-167° C. A characteristic infraredmaximum appeared at 1752 cm⁻¹ (C═O; s). A toluene solution of theproduct spotted on silica gel developed an intense purple-colored image.

C. In a manner similar to that described in part B above, 3.35 g (0.01mole) of 2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]-benzoic acid and2.42 g (0.011 mole) of N,N,N',N'-tetraethyl-m-phenylenediamine wereinteracted to obtain3-[2,4-bis(diethylamino)phenyl-3-(1-n-butyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ; R⁵═CH₃ ; R⁶ ═(CH₂)₃ CH₃), as tan-colored crystals which melted at 78°-80°C. A toluene solution of the product spotted on silica gel developed anintense blue-black-colored image.

EXAMPLE 5

A. In a manner similar to that described in part A of Example 1hereinabove, 7.4 g (0.05 mole) of phthalic anhydride, 16.0 g (0.053mole) of 76.5 percent active 1-n-octyl-2-methylindole, and 13.3 g (0.1mole) of aluminum chloride were interacted in 50 ml of benzene to obtain6.9 g of 2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]benzoic acid (FormulaVIII: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═(CH₂)₇ CH₃), as apink-colored powder which melted at 121°-123° C. The nuclear magneticspectrum was in agreement with the structure and a significant maximaoccurred at 1717 cm⁻¹ (C═O; s).

B. Proceeding in a manner similar to that described in part B of Example4 above, 3.91 g (0.01 mole) of2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]benzoic acid, 1.80 g (0.011mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and five ml of aceticanhydride were interacted at ambient temperature for a period ofapproximately 24 hours to obtain, after recrystallization from methanol,3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-octyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶═(CH₂)₇ CH₃) which melted over the range 64°-68° C. A significantinfrared absorption was observed at 1750 cm⁻¹ (C═O; s). Analysis by massspectrum showed m/e peaks at 537 (M⁺) and 493 (M⁺ --CO₂). A toluenesolution of the product when spotted on a phenolic resin coated paperdeveloped an intense grape-colored image.

EXAMPLE 6

A. Proceeding in a manner similar to that described in part A of Example2, 14.3 g (0.05 mole) of tetrachlorophthalic anhydride, 16.0 g (0.07mole) of 76 percent active 1-n-butyl-2-methylindole and 13.3 g (0.10mole) of aluminum chloride were interacted in 100 ml of benzene. Thereaction mixture was drowned in 200 ml of five percent hydrochloric acidwith stirring. The solid which formed was collected by filtration,washed with water and dried to obtain2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid (Formula VIII: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ =(CH₂)₃ CH₃),a pale yellow solid melting at 162°-164° C. The nuclear magneticresonance spectrum was in accord with the structure.

B. A mixture of 5.20 g (0.01 mole) of2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared in part A above, 2.0 g (0.012 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and five ml of acetic anhydridewas warmed over a period of approximately forty minutes at 110° C. Thereaction mixture was then cooled to ambient temperature, set asideovernight, rendered alkaline with 10 percent aqueous sodium hydroxidesolution and extracted with benzene. Petroleum ether was slowly added tothe separated benzene extract and the solid which slowly separated wascollected by filtration and dried to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-butyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶═(CH₂)₃ CH₃ ; Y¹ ═H), as white crystals having a melting point of173°-175° C. The nuclear magnetic resonance spectrum was consistent withthe structure; a maximum of 1770 cm⁻¹ (C═O; s) appeared in the infraredspectrum; the spectrum showed a m/e peak at 617 (M⁺, 4 Cl).

EXAMPLE 7

A. Proceeding in the same manner as that described in part A of Example6 above, 14.3 g (0.05 mole) of tetrachlorophthalic anhydride, 16.0 g(0.052 mole) of 76.5 percent active 1-n-octyl-2-methylindole and 13.3 g(0.10 mole) of aluminum chloride were interacted to obtain2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid (Formula VIII: R^(o) ═R¹ ═R² ═R³ ═Cl; R⁵ ═CH₃ ; R⁶ ═(CH₂)₇ CH₃ ; Y¹═H), a pale orange solid melting at 132°-134° C. The infrared spectrum,showing a maximum at 1745 cm⁻¹ (C═O; s) and the nuclear magneticresonance spectrum was in accord with the structure.

B. A mixture of 2.64 g (0.005 mole) of2-[1-n-octyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared as described in part A above, 1.0 g (0.006 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and three ml of aceticanhydride were interacted as described in Example 2, part C above toobtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-octyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorphthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁵ ═CH₃ ; R⁶═(CH₂)₇ CH₃ ; Y¹ ═H), a pale yellow powder melting at 145°-147° C. Theinfrared spectrum showed a maximum appearing at 1770 cm⁻¹ (C═O; s) andthe nuclear magnetic resonance spectrum was concordant with thestructure.

EXAMPLE 8

A. A suspension of 14.8 g (0.10 mole) of phthalic anhydride, 10.5 g(0.05 mole) of 2-phenylindole and 82 ml of xylene was heated to 110° C.briefly, cooled to and maintained at 95° C. for approximately two hours.The solution was cooled to ambient temperature and the solid whichseparated was collected by filtration and dried to obtain 10.6 g of2-[(2-phenyl-3-indolyl)carbonyl]benzoic acid (Formula VIII: R^(o) ═R¹═R² ═R³ ═R⁶ ═Y¹ ═H; R⁵ ═C₆ H₅) which melted at 106°-107° C. and had anuclear magnetic resonance spectrum consistent with the assignedstructure.

B. A mixture of 4.82 g (0.014 mole) of the2-[(2-phenyl-3-indolyl)carbonyl]benzoic acid from part A above, 3.60 g(0.02 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine, and five ml ofacetic anhydride was slowly heated until a purple color formed andmaintained at this temperature for approximately two hours. Aftercooling to room temperature, sufficient 3 N hydrochloric acid was addedto the mixture to effect solution and stirring was continued forapproximately 1.5 hours. The resulting solution was filtered and the pHadjusted to five by the addition of sodium acetate. The precipitatewhich separated from the solution was collected by filtration and driedto obtain3-[2,4-bis(dimethylamino)phenyl]-3-(2-phenyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═R⁶ ═Y¹ ═H; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁵ ═C₆H₅). After recrystallization from toluene and hexane, the offwhite-colored solid melted at 153°-155° C. Significant infrared maximawere observed at 3380 cm⁻¹ (NH; m) and 1750 cm⁻¹ (C═O; s). The nuclearmagnetic resonance spectrum was consistent with the structure. A toluenesolution of this product spotted on silica gel developed an intensegrape-red-colored image.

EXAMPLE 9

A. Proceeding in a manner similar to part A of Example 8, butsubstituting 2-methylindole for 2-phenylindole, there was obtained2-[(2-methyl-3-indolyl)carbonyl]benzoic acid (Formula VIII: R^(o) ═R¹═R² ═R³ ═R⁶ ═Y¹ ═H; R⁵ ═CH₃), as pale pink-colored crystals melting at198°-200° C.

B. A mixture of 8.37 g (0.03 mole) of2-[(2-methyl-3-indolyl)carbonyl]benzoic acid, prepared as described inpart A above, 8.37 g (0.05 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 10 ml of acetic anhydridewas interacted at 50° C. as described in part B of Example 8 above toobtain 3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═R⁶ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂).After purification by slurrying in a benzene and ligroin mixture, thecollected and dried product melted at 183°-186° C. The product had massspectrum with a m/e peak at 425 (M⁺). Both the infrared and nuclearmagnetic resonance spectra were consistent with this structure. Atoluene solution of the product spotted on a phenolic resin coated paperdeveloped an intense grape-colored image.

EXAMPLE 10

A. A mixture of 5.0 g (0.03 mole) of 5-methoxy-2-methylindole and 4.6 g(0.03 mole) of phthalic anhydride in 25 ml of ethylene dichloride wasrefluxed for ten hours, cooled to room temperature and the separatedsolid was collected by filtration and dried to obtain2-[(2-methyl-5-methoxy-3-indolyl)carbonyl]-benzoic acid (Formula VIII:R^(o) ═R¹ ═R² ═R³ ═R⁶ ═H; R⁵ ═CH₃ ; Y¹ ═OCH₃), as a pale pink-coloredsolid which decomposed at 203°-204° C. The nuclear magnetic resonanceand infrared spectra were consistent with the assigned structure.

B. A mixture of 2.0 g (0.006 mole) of2-[(2-methyl-5-methoxy-3-indolyl)carbonyl]benzoic acid, obtained asdescribed in part A above, 1.1 g (0.0067 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and six ml of acetic anhydridewere interacted at 50°-55° C. in a manner similar to that described inExample 2, part B to obtain 2.5 g of3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-5-methoxy-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═R⁶ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹═OCH₃), as a light pink-colored solid melting at 196°-198° C. withdecomposition. The infrared spectrum, showing a significant maximum at1740 cm⁻¹ (C═O; s) and the nuclear magnetic resonance spectrum were inaccord with the structure. A toluene solution of this product spotted ona phenolic resin coated paper developed an intense violet-colored image.

EXAMPLE 11

A. A mixture of 5.0 g (0.034 mole) of phthalic anhydride and 5.0 g(0.034 mole) of 2,5-dimethylindole in 30 ml of ethylene dichloride wasrefluxed for 20 hours, cooled and the separated solid filtered off anddried to obtain 3.8 g of 2-[(2,5-dimethyl-3-indolyl)carbonyl]benzoicacid (Formula VIII: R^(o) ═R¹ ═R² ═R³ ═R⁶ ═H; R⁵ ═CH₃ ; Y¹ ═CH₃) as apink-colored solid melting at 198°-200° C.

B. A mixture of 2.0 g (0.007 mole) of2-[(2,5-dimethyl-3-indolyl)carbonyl]benzoic acid from part A above, 1.1g (0.007 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and seven mlof acetic anhydride was interacted in a manner similar to that describedin Example 3, part E above, to obtain 2.35 g of3-[2,4-bis(dimethylamino)phenyl]-3-(2,5-dimethyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R³ ═R⁶ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹ ═CH₃),a light purple solid melting over the range of 100°-125° C. The infraredshowed a characteristic absorption maximum at 1760 cm⁻¹ (C═O; s). Atoluene solution of this product spotted on acid clay or phenolic resindeveloped an intense violet-colored image.

EXAMPLE 12

A mixture of 1.55 g (0.0036 mole) of2-[(1,2-dimethyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acidprepared in a manner similar to part A of Example 2, 0.58 g (0.0035mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and ten ml of aceticanhydride was heated to reflux for approximately one hour. After coolingto room temperature, the reaction mixture was poured into 20 ml of 10percent hydrochloric acid and the mixture then rendered alkaline by theaddition of concentrated ammonium hydroxide. The purple solid whichseparated was collected by filtration, dried, and recrystallized twicefrom isopropyl acetate to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁵ ═R⁶ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹═H) which decomposed at 228°-229° C. The mass spectrum showed an m/e at575 (M⁺, 4 Cl). A toluene solution of the product spotted on silica geldeveloped an intense purple-colored image.

EXAMPLE 13

A suspension of 1.36 g (0.01 mole) of m-amino-N,N-dimethylaniline in 20ml of acetic anhydride was heated to 80°-90° C. for approximately thirtyminutes and then cooled to room temperature. Three grams (0.01 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A of Example 1, was added and the resulting mixturewas heated at 60°-70° C. for approximately thirty minutes. Aftercooling, the reaction mixture was poured into 100 ml of 10 percenthydrochloric acid and the mixture made akaline with 10 percent aqueoussodium hydroxide with the addition of ice. The solid which separated wascollected by filtration and dried to obtain3-[2-acetamido-4-dimethylaminophenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; ##STR32## R═R⁵ ═CH₃ ; R⁶ ═CH₂CH₃) as a pale blue-colored solid melting over the range 180°-195° C.Infrared absorption maxima appeared at 1757 cm⁻¹ (C═O; s) and 1696 cm⁻¹(C═O; s).

EXAMPLE 14

A mixture of 0.34 g (0.001 mole) of2-[(1,2-dimethyl-3-indolyl)carbonyl]-5-dimethylaminobenzoic acidprepared as described in Example 1 of U.S. Pat. No. 3,540,910 wasinteracted with 0.16 g (0.001 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine in 5 ml of acetic anhydride ina similar manner to the procedure described in Example 1, part Chereinabove to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolyl)-6-dimethylaminophthalide(Formula III: R^(o) ═R¹ ═R³ ═Y¹ ═H; R² ═N(CH₃)₂ ; R═R⁵ ═R⁶ ═CH₃ ; R⁴═N(CH₃)₂) which melts over the range of 146°-152° C. A significantinfrared absorption maximum appeared at 1760 cm⁻¹ (C═O; s). A toluenesolution of this product spotted on silica gel developed an intensegrape-red-colored image.

EXAMPLE 15

A. To a mixture of 8.17 g (0.05 mole) of N-ethylcarbazole and 3.7 g(0.025 mole) of phthalic anhydride in 112 g of chlorobenzene, 6.65 g(0.05 mole) of aluminum chloride was added in small increments atambient temperature after which the mixture was warmed in the range of50°-70° C. for two hours. The reaction mixture was poured onto ice andrendered acidic by the addition of 10 percent hydrochloric acid. Thechlorobenzene layer was separated and steam-distilled to remove thechlorobenzene. The residue was extracted with 10 percent aqueous sodiumhydroxide, filtered to remove the insolubles and then acidified withdilute hydrochloric acid. The solid which separated was collected byfiltration, washed with water and dried to obtain2-[(9-ethyl-3-carbazolyl)carbonyl]benzoic acid (Formula VII: R^(o) ═R¹═R² ═R³ ═H; R⁸ ═CH₂ CH₃) melting over the range 120°-130° C.

B. A mixture of 3.43 g (0.01 mole) of2-[(9-ethyl-3-carbazolyl)carbonyl]benzoic acid, 1.80 g (0.011 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 4.0 ml of acetic anhydridewas interacted in a manner similar to that described in Example 1, partC above to yield3-[2,4-(dimethylamino)phenyl]-3-(9-ethyl-3-carbazolyl)phthalide (FormulaV: R^(o) ═R¹ ═R² ═R³ ═H; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁸ ═CH₂ CH₃) which meltedover the range 134°-142° C. A significant infrared absorption maximumappeared at 1753 cm⁻¹ (C═O; s). A toluene solution of this productspotted on silica gel developed a bordeaux-colored image.

EXAMPLE 16

A. To a mixture of 2.96 g (0.02 mole) of phthalic anhydride and 5.72 g(0.04 mole) of N-phenylpyrrole in 50 ml of chlorobenzene, maintained at0°-5° C. in an ice bath, 810 g (0.06 mole) of aluminum chloride wasadded in small portions. The reaction mixture was held at 0°-5° C. forapproximately two hours. The reaction was allowed to warm to roomtemperature and then set aside overnight at ambient temperature. Thereaction mixture was worked up in a manner similar to that described inpart A of Example 15 to obtain 2-[(1-phenyl-2-pyrrolyl)carbonyl]benzoicacid (Formula IX: R^(o) ═R¹ ═R² ═R³ ═H; R⁷ ═C₆ H₅) which melted over therange 159°-168° C.

B. A mixture of 2.91 g (0.01 mole) of2-[(1-phenyl-2-pyrrolyl)carbonyl]benzoic acid prepared in part A above,2.34 g (0.017 mole) of 84.6 percent activeN,N,N',N'-tetramethyl-m-phenylenediamine in 4.0 ml of acetic anhydridewas interacted in a manner similar to that described in Example 1, partC to obtain 2.61 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-phenyl-2-pyrrolyl)phthalide(Formula IV: R^(o) ═R¹ ═R² ═R³ ═H; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁷ ═C₆ H₅), apeach-colored powder melting at 193°-194° C. The infrared spectrumshowed a maximum at 1760 cm⁻¹ (C═O; s). A toluene solution of thisproduct spotted on silica gel developed an immediate orange-red-coloredimage.

EXAMPLE 17

A. Proceeding in a manner similar to that described in part A of Example16, 14.8 g (0.1 mole) of phthalic anhydride, 16.2 g (0.2 mole) ofN-methylpyrrole and 39.0 g (0.3 mole) of aluminum chloride wereinteracted in 50 ml of chlorobenzene to obtain2-[(1-methyl-2-pyrrolyl)carbonyl]benzoic acid (Formula IX: R^(o) ═R¹ ═R²═R³ ═H; R⁷ ═CH₃) melting at 165°-167° C. A significant infraredabsorption maximum appeared at 1710 cm⁻¹ (C═O; s).

B. A mixture of 4.58 g (0.02 mole) of2-[(1-methyl-2-pyrrolyl)carbonyl]benzoic acid, from part A above, 3.61 g(0.022 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and 3.0 ml ofacetic anhydride was interacted in a manner similar to that describedabove in Example 1, part C to obtain 1.92 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-methyl-2-pyrrolyl)phthalide(Formula IV: R^(o) ═R¹ ═R² ═R³ ═H; R═R⁷ ═CH₃ ; R⁴ ═N(CH₃)₂), a tanpowder melting at 148°-150° C. A toluene solution of this productspotted on silica gel developed an intense red-colored image.

EXAMPLE 18

A. A stirred solution of 48.0 g (0.250 mole) of trimellitic anhydrideand 45.0 g (0.314 mole) of 1-ethyl-2-methylindole in 350 ml of ethylenedichloride was heated at reflux for a period of approximately two hours,and then allowed to cool to ambient temperature. The solid, whichseparated, was collected by filtration, washed with 200 ml of ethylenedichloride and dried in vacuo at 60° C. to obtain 66.0 g of4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid(Formula VIII: R¹ ═R² ═H/COOH; R^(o) ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃),a yellowish-orange solid melting over the range 198°-201° C. Infraredmaxima appeared at 1730 (C═O; s) and 1700 cm⁻¹ (C═O; vs). The nuclearmagnetic resonance spectrum was in agreement with the assignedstructure.

B. A stirred mixture of 17.5 g (0.05 mole) of the4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,prepared as described in part A above, 8.5 g (0.052 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 25 ml of acetic anhydridewas heated at 50° C. for a period of two hours and then allowed to coolto ambient temperature. After the addition of 25 ml of isopropylalcohol, the resulting mixture was poured into water with vigorousstirring. The solid which separated was collected by filtration, washedwith water and dried in vacuo at 60° C. to obtain 22.0 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-3-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═N(CH₃)₂; R⁶ ═CH₂ CH₃) as a dark purple solid melting over the range 149°- 151°C. Infrared maxima appeared at 1775 (C═O; s) and 1720 cm⁻¹ (C═O; s).

C. Three milliliters of dimethyl sulfate was added to a refluxingmixture of 3.0 g of the3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part B above, 3.0 g of potassium carbonate and100 ml of acetone. The reaction mixture was heated at reflux for aperiod of two hours and was then poured into water and the aqueousmixture extracted with toluene. The toluene extract was washedsuccessively with water and saturated salt solution and then evaporatedto dryness. The residue was triturated with ligroin (b.p. 60°-90° C.)and the solid separated and dried to obtain 1.0 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴═N(CH₃)₂ ; R⁶ ═CH₂ CH₃), a light purple solid melting over the range72°- 85° C. Infrared maxima appeared at 1760 (C═O; s) and 1730 cm⁻¹(C═O; s). Analysis by mass spectrum showed m/e peaks at 511 (M⁺) and at452 (M⁺ --CO₂ CH₃). A toluene solution of the produce spotted on silicagel, an acidic clay or a phenolic resin developed a grape-colored image.

EXAMPLE 19

To a stirred mixture of 6.38 g (0.013 mole) of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,prepared as described above in part B of Example 18, 150 ml ofhexamethylphosphoramide and 10 ml of 25 percent aqueous sodiumhydroxide, there was added 7.0 ml of ethyl iodide. The mixture wasstirred at room temperature for a period of two hours. The reactionmixture was then drowned in water and the aqueous mixture was extractedwith toluene. The toluene layer was washed with water, dried overanhydrous sodium sulfate, and evaporated. The residue was trituratedwith ligroin (b.p. 60°-90° C.) and the separated solid collected anddried to obtain 0.92 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ CH₃ ; R⁴═N(CH₃)₂ ; R⁶ ═ CH₂ CH₃), a light brown powder melting over the range88°-97° C. Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O;s). The nuclear magnetic resonance spectrum was in agreement with theassigned structure. Analysis by mass spectrum showed m/e peak at 525(M⁺). A toluene solution of the product spotted on silica gel, an acidicclay or a phenolic resin developed a grape-colored image.

EXAMPLE 20

Following a procedure similar to that described above in part C ofExample 18 but substituting dimethylformamide for acetone and n-octylbromide for dimethyl sulfate, there was obtained3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COO(CH₂)₇ CH₃ ; R⁴═N(CH₃)₂ ; R² ═CH₂ CH₃) as a light brown oil. Infrared maxima appearedat 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). A benzene solution of theproduct spotted on silica gel, an acidic clay or a phenolic resindeveloped a grape-colored image.

EXAMPLE 21

Following a procedure similar to that described above in Example 20except that α-bromotoluene was used in place of n-octyl bromide, therewas obtained 2.52 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide (Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R²═H/COOCH₂ C₆ H₅ ; R⁴ ═N(CH₃)₂ ; R⁶ ═CH₂ CH₃), a light purple powdermelting over the range 72°-78° C. Infrared maxima appeared at 1770 cm⁻¹(C═O; s). Analysis by mass spectrum showed m/e peaks at 587 (M⁺) and 543(M⁺ --CO₂). A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a grape-colored image.

EXAMPLE 22

A. A mixture of 35 g (0.10 mole) of4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acidprepared as described in Example 18, part A above, 20 g (0.103 mole) ofN,N-diethyl-m-phenetidine and 60 ml of acetic anhydride was stirred atroom temperature for a period of approximately eighteen hours. After theaddition of 100 ml of isopropyl alcohol, the resulting mixture waspoured into water with vigorous stirring. The solid which separated wascollected by filtration, washed with water and dried to obtain 53.4 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═OC₂ H₅; R⁵ ═CH₃), a dark blue solid melting over the range of 130°-144° C.Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 526 (M⁺) and 481 (M⁺ --CO₂H).

B. Employing a procedure similar to that described in part C of Example18, but interacting 5.0 g (0.0095 mole) of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-3-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A of this example with dimethyl sulfateinstead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,there was obtained 4.9 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═OC₂H₅ ; R⁵ ═CH₃), a light green-colored solid melting over the range96°-103° C. Infrared maxima appeared at 1765 (C═O; s) and 1730 cm⁻¹(C═O; s). The nuclear magnetic resonance spectrum was in agreement withthe assigned structure. Analysis by mass spectrum showed m/e peaks at540 (M⁺), 496 (M⁺ --CO₂) and 418 (M⁺ --COOCH₃). A toluene solution ofthe product spotted on silica gel, an acidic clay or a phenolic resindeveloped a deep blue-colored image which had good lightfastness.

EXAMPLE 23

When diethyl sulfate was substituted for dimethyl sulfate forinteraction with3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideaccording to the procedure described in part B of Example 22, there wasobtained 1.5 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ CH₃ ; R⁴═OC₂ H₅ ; R⁵ ═CH₃ ;), a light yellow solid melting over the range141°-148° C. Infrared maxima appeared at 1750 (C═O; s) and 1732 cm⁻¹(C═O; s). Analysis by mass spectrum showed m/e peaks at 554 (M⁺), 510(M⁺ --CO) and 481 (M⁺ --CO₂ C₂ H₅). A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed adeep blue-colored image which had good lightfastness.

EXAMPLE 24

Following a procedure similar to that described above in Example 22,part B, 5.0 g (0.0095 mole) of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 22, part A was interacted with 2.0 g(0.0117 mole) of α-bromotoluene to obtain 3.4 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ C₆ H₅ ;R⁴ ═OC₂ H₅ ; R⁵ ═CH₃), a light yellow solid melting over the range82°-87° C. Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O;s). Analysis by mass spectrum showed m/e peaks at 616 (M⁺) and 572 (M⁺--CO₂). A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a deep blue-colored imagewhich had good lightfastness.

EXAMPLE 25

When n-octyl bromide was substituted for α-bromotoluene for interactionwith3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideaccording to the procedure described in Example 24, there was obtained3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-octoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COO-n--(CH₂)₇CH₃ ; R⁴ ═OC₂ H₅ ; R⁵ ═CH₃), a light blue solid melting over the range134°-162° C. A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a deep blue-colored imagewhich had good lightfastness.

EXAMPLE 26

Substituting 1-bromohexadecane for n-octyl bromide for interaction with3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideaccording to the procedure described in Example 25, there was obtained7.1 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-hexadecanoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H/COO(CH₂)₁₅ CH₃ ; R⁴ ═OC₂ H₅; R⁵ ═CH₃), a light brown oil. Infrared maxima appeared at 1765 (C═O; s)and 1725 cm⁻¹ (C═O; s). The nuclear magnetic resonance spectrum was inagreement with the assigned structure. Analysis by mass spectrum showedm/e peaks at 750 (M⁺) and 706 (M⁺ --CO₂). A benzene solution of theproduct spotted on silica gel, an acidic clay or phenolic resindeveloped a deep blue-colored image which had good lightfastness.

EXAMPLE 27

To a stirred solution of 5.3 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 22, part A, in 25 ml of acetone therewas added 2.6 g of 1,1,3,3-tetramethylbutylamine. The mixture wasstirred at ambient temperature for approximately ten minutes and then160 ml of n-hexane was added. The supernatant liquid was decanted andthe insoluble, brown, gummy residue triturated with n-hexane to obtain6.2 g of the 1,1,3,3-tetramethylbutylammonium salt of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: ##STR33## R═R⁶ ═C₂ H₅ ; R⁴ ═OC₂ H₅ ; R⁵ ═CH₃), abeige-colored solid melting over the range of 80°-105° C. withdecomposition. Infrared spectral analysis showed significant maxima inthe range from 2350 cm⁻¹ to 2150 cm⁻¹, and a strong absorption at 1760cm⁻¹ (C═O, s). The assinged structure was corroborated by a concordantnuclear magnetic resonance spectrum. A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed adeep blue-colored image which had good lightfastness. This product isalso a water-soluble color-former.

EXAMPLE 28

A. Following a procedure similar to that described in part A of Example22 but interacting N,N-dimethylaniline instead ofN,N-diethyl-m-phenetidine, with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁶ ═C₂H₅), a blue-colored solid melting over the range 141°-160° C. Infraredmaxima appeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). Analysis bymass spectrum showed m/e peaks at 454 (M⁺), 410 (M⁺ --CO₂) and 409 (M⁺--COOH).

B. Employing a procedure similar to that described in part C of Example18, but substituting3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above for3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁶═C₂ H₅), a light yellow solid melting over the range 101°-110° C.Infrared maxima appeared at 1760 (C═O; s) and 1730 cm⁻¹ (C═O; s). Thenuclear magnetic resonance spectrum was in agreement with the assignedstructure. Analysis by mass spectrum showed m/e peaks at 468 (M⁺), 424(M⁺ --CO₂) and 409 (M⁺ --COOCH₃). A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed ablue-colored image had good lightfastness.

EXAMPLE 29

Proceeding in a manner similar to that described above in Example 23,3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 28, part A, was interacted with diethylsulfate to obtain3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOC₂ H₅ ; R⁶═C₂ H₅), a light green solid melting over the range 114°-131° C.Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 482 (M⁺), 438 (M⁺ --CO₂)and 409 (M⁺ --CO₂ C₂ H₅). A toluene solution of the product spotted onsilica gel, an acidic clay or a phenolic resin developed a blue-coloredimage which had good lightfastness.

EXAMPLE 30

When α-bromotoluene was substituted for diethyl sulfate in Example 29,there was obtained3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ C₆ H₅ ;R⁶ ═C₂ H₅), a light green-colored solid melting over the range 93°-98°C. Infrared maxima appeared at 1770 (C═O; s) and 1728 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 544 (M⁺) and 500 (M⁺--CO₂). A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a blue-colored image which hadgood lightfastness.

EXAMPLE 31

A. Following a procedure similar to that described in part A of Example22, but using 15 g of N,N-diethylaniline instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁵═CH₃), a blue solid melting over the range 169°-182° C. Infrared maximaappeared at 1765 (C═O; s) and 1730 cm⁻¹ (C═O; s). The nuclear magneticresonance spectrum was in agreement with the assigned structure.

B. Proceeding in a manner similar to that described in part C of Example18, but using3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above in place of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5,6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6;l-methoxycarbonylphthalide (Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═R⁴ ═Y¹═H; R¹ ═R² ═H/COOCH₃ ; R⁵ ═CH₃), a light green solid melting over therange 114°-128° C. Infrared maxima appeared at 1765 (C═O; s) and 1730cm⁻¹ (C═O; s). A toluene solution of the product spotted on silica gel,an acidic clay or a phenolic resin developed a blue-colored image whichhad good lightfastness.

EXAMPLE 32

A. Employing a procedure similar to that described in part A of Example22, but using m-chloro-N,N-dimethylaniline instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-chloro-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═Cl; R⁶═C₂ H₅), as a greenish-blue solid melting over the range 130°-142° C.Infrared maxima appeared at 1770 (C═O; s) and 1725 cm⁻¹ (C═O; m).

B. Proceeding in a manner similar to that described in part C of Example18, but using3-(2-chloro-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(2-chloro-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═Cl;R⁶ ═C₂ H₅), as a light blue solid melting over the range 168°-193° C.Infrared maxima appeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). Atoluene solution of the product spotted on silica gel, an acidic clay ora phenolic resin developed a pale green-colored image.

EXAMPLE 33

A. Following a procedure similar to that described in part A of Example22, but using N,N-m-diethyltoluidine instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═R⁵═CH₃), a turquoise-colored solid melting over the range 146°-162° C.Infrared maxima appeared at 1765 (C═O; s) and 1720 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 496 (M⁺), 452 (M⁺ --CO₂)and 451 (M⁺ --COOH).

B. Employing a procedure similar to that described in part C of Example18, but using2-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,there was obtained3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═R⁵═CH₃), a light yellow solid melting over the range 113°-120° C. Infraredmaxima appeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). The nuclearmagnetic resonance spectrum was in agreement with the assignedstructure. Analysis by mass spectrum showed m/e peaks at 510 (M⁺) and495 (M⁺ --COOCH₃). A toluene solution of the product spotted on silicagel, an acidic clay or a phenolic resin developed a turquoise-coloredimage which had good lightfastness.

EXAMPLE 34

Proceeding in a manner similar to that described above in Example 23,3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 33, part A was interacted with diethylsulfate to obtain3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOC₂ H₅ ; R⁴═R⁵ ═CH₃), a tan solid melting over the range 89°-144° C. Infraredmaxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s). Analysis bymass spectrum showed m/e peaks at 524 (M⁺), 480 (M⁺ --CO₂) and 451 (M⁺--CO₂ C₂ H₅). A toluene solution of the product spotted on silica gel,an acidic clay or a phenolic resin developed a torquoise-colored imagewhich had good lightfastness.

EXAMPLE 35

When α-bromotoluene was substituted for diethyl sulfate in Example 34for interaction with3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 33, part A, there was obtained3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ C₆ H₅ ;R⁴ ═R⁵ ═CH₃), a light yellow solid melting over the range 92°-98° C.Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 586 (M⁺) and 542 (M⁺--CO₂). A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a turquoise-colored imagehaving good lightfastness.

EXAMPLE 36

A. Following a procedure similar to that described in part A of Example22, but using N,N-di-n-butylaniline instead of N,N-diethyl-m-phenetidinefor interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═CH₂ (CH₂)₂ CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOH;R⁵ ═CH₃ ; R⁶ ═C₂ H₅), as a blue-colored solid melting over the range81°-94° C. Infrared maxima appeared at 1760 (C═O; s) and 1725 cm⁻¹ (C═O;m).

B. Employing a procedure similar to that described in part C of Example18 but using3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═CH₂ (CH₂)₂ CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃; R⁵ ═CH₃ ; R⁶ ═C₂ H₅), a light yellow solid melting over the range72°-94° C. Infrared maxima appeared at 1765 (C═O; s) and 1728 cm⁻¹ (C═O;s). Analysis by mass spectrum showed m/e peaks at 552 (M⁺), 508 (M⁺--CO₂) and 493 (M⁺ --CO₂ CH₃). A toluene solution of the product spottedon silica gel, an acidic clay or a phenolic resin developed ablue-colored image which had good lightfastness.

EXAMPLE 37

A. Following a procedure similar to that described in part A of Example22, but using N,N-dimethyl-m-anisidine instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-methoxy-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═OCH₃ ;R⁶ ═C₂ H₅), a deep blue solid melting over the range 128°-133° C.Infrared maxima appeared at 1760 (C═O; s) and 1730 cm⁻¹ (C═O; m).Analysis by mass spectrum showed m/e peaks at 484 (M⁺), 440 (M⁺ --CO₂)and 439 (M⁺ --COOH).

B. Employing a procedure similar to that described in part C of Example18, but using3-(2-methoxy-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained2-(2-methoxy-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═OCH₃; R⁶ ═C₂ H₅), as a light blue solid melting over the range 131°-135° C.Infrared maxima appeared at 1760 (C═O; s) and 1730 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 498 (M⁺), 454 (M⁺ --CO₂)and 439 (M⁺ -- CO₂ CH₃). A toluene solution of the product spotted onsilica gel, an acidic clay or a phenolic resin developed a deepblue-colored image which has good lightfastness.

EXAMPLE 38

A. Proceeding in a manner similar to that described in part A of Example22, but using 3-n-butoxy-N,N-diethylaniline instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-n-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═OCH₂(CH₂)₂ CH₃ ; R⁵ ═CH₃), a deep blue solid melting over the range113°-125° C. Infrared maxima appeared at 1760 (C═O; s) and 1725 cm⁻¹(C═O; m). Analysis by mass spectrum showed a m/e peak at 510 (M⁺ 13CO₂).

B. Following a procedure similar to that described in part C of Example18, but using3-(2-n-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)-phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(2-n-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴═OCH₂ (CH₂)₂ CH₃ ; R⁵ ═CH₃), a light green oil. Infrared maxima appearedat 1765 (C═O; s) and 1730 cm⁻¹ (C═O; s). A toluene solution of theproduct spotted on silica gel, an acidic clay or a phenolic resindeveloped a deep blue-colored image which had good lightfastness.

EXAMPLE 39

A. A stirred mixture of 19.2 g (0.10 mole) of trimellitic anhydride, 35g (0.22 mole) of 1-ethyl-2-methylindole and 75 ml of acetic anhydridewas heated at reflux for approximately one hour, then cooled slightlybelow reflux after which there was slowly added 100 ml of methanol. Theresulting solution was cooled to ambient temperature and slowly pouredwith stirring into a mixture of ice and water. The solid that formed wascollected by filtration and dried in vacuo at 60° C. to obtain3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide (Formula VI: R¹═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R^(o) ═R³ ═Y¹═Y^(1') H); as a deep red solid melting over the range of 110°-119° C.Infrared maxima appeared at 1760 (C═O; s) and 1720 cm⁻¹ (C═O; m). Thenuclear magnetic resonance spectrum was in accord with the assignedstructure.

B. Following a procedure similar to that described above in part C ofExample 18, but using3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared asdescribed above in part A of this example instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOCH₃ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H; R⁵ ═R^(5')═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃), a tan solid melting over the range of226°-229° C. with decomposition. Infrared maxima appeared at 1765 (C═O;s) and 1735 cm⁻¹ (C═O; s). The nuclear magnetic resonance spectrum wasconcordant with the assigned structure. Mass spectrum analysis showedm/e peaks at 506 (M⁺), 462 (M^(+--CO) ₂) and 447 (M⁺ --CO₂ CH₃). Anacetone solution of the product spotted on silica gel, an acidic clay ora phenolic resin developed a deep red-colored image which had goodxerographic copiability and good lightfastness.

EXAMPLE 40

A stirred mixture of 3.0 g (0.006 mole) of3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalideprepared as in Example 39, part B and 35 ml of3-(di-n-butylamino)propylamine was heated at 125°-130° C. forapproximately five hours and then allowed to cool to ambienttemperature. The brown solution was poured into a mixture of water andtoluene and the toluene layer was separated, washed with water andconcentrated under reduced pressure. The excess amine was removed byvacuum distillation. There was thus obtained3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-(3-N,N-di-n-butylamino)propylaminocarbonylphthalide(Formula VI: R¹ ═R² ═H/CONH(CH₂)₃ N(h-C₄ H₉)₂ ; R⁵ ═R^(5') ═CH₃ ; R⁶═R^(6') ═C₂ H₅ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H), as a light brown oil.Infrared maxima appeared at 1770 (C═O; s) and 1650 cm⁻¹ (C═O; s). Thenuclear resonance spectrum was concordant with the assigned structure.When a soy oil solution of the product was spotted on silica gel, anacidic clay or a phenolic resin, a dark red-colored image developedwhich had good lightfastness.

EXAMPLE 41

A. Following a procedure similar to that described in Example 18, part Babove, for interacting 10.6 g of4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,prepared as described in Example 18, part A, and 7.0 g of1-n-butyl-2-methylindole, there was obtained 16 g of3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula VI: R¹ ═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6') ═n-C₄H₉ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H), a deep red solid melting over the rangeof 128°-138° C. with decomposition. Infrared maxima appeared at 1762(C═O; s) and 1738 cm⁻¹ (C═O; s).

B. Employing a procedure similar to that described above in part B ofExample 39, except that3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described above in part A of this example was used in placeof 3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide, there wasobtained3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOCH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6')═n--C₄ H₉ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H), a light orange solid melting overthe range of 82°-94° C. Significant infrared maxima appeared at 1765(C═O; s) and 1730 cm⁻¹ (C═O; s). Mass spectral analysis showed m/e peaksat 534 (M⁺) and 490 (M⁺ --CO₂). A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed adeep red-colored image which possessed good lightfastness.

EXAMPLE 42

A. Proceeding in a manner similar to that described in Example 41, partA above, but using 1-allyl-2-methylindole instead of1-n-butyl-2-methylindole for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula VI: R¹ ═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6') ═CH₂--CH═CH₂ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H), a deep red solid melting at 135°C. with decomposition. Significant infrared maxima appeared at 1765(C═O; s) and 1730 cm⁻¹ (C═O; m).

B. When3-(1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A of this example was substituted for3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide in theprocedure described in part B of Example 39, there was obtained3-(1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOCH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6') ═CH₂--CH═CH₂ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H), an orange solid melting over therange of 152°-164° C. Infrared spectral analysis showed maxima at 1760(C═O; s) and 1732 cm⁻¹ (C═O; s). Nuclear magnetic resonance analysis wasin accord with the assigned structure. Analysis by mass spectrum showedm/e peaks at 518 (M⁺), 474 (M⁺ --CO₂) and 459 (M⁺ --COOCH₃). A toluenesolution of the product spotted on silica gel, an acid clay or aphenolic resin developed a deep red-colored image which had goodlightfastness.

EXAMPLE 43

Employing a procedure similar to that described in Example 18, part Babove, for interacting4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,prepared as described in Example 18, part A and 1-ethyl-2-methylindole,there was obtained3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide (Formula VI: R¹═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R^(o) ═R³ ═Y¹═Y^(1') ═H). Proceeding in a manner similar to that described in Example39, part B, the following esters of the thus prepared3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide of Formula VI(R^(o) ═R³ ═Y¹ ═Y^(1') ═H; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R¹/R² ═H/COOH) above were prepared by esterification employing theappropriate dialkyl sulfate or organic halide. A toluene solution ofthese individual esters, when spotted on silica gel, an acidic clay or aphenolic resin, each developed a deep red-colored image which had goodlightfastness. The infrared analyses, nuclear magnetic resonanceanalyses and mass spectral analyses obtained for the products ofExamples 44 to 48 inclusive were concordant for the assigned structuregiven in those examples.

EXAMPLE 443,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide

(Formula VI: R¹ ═R² ═H/COOC₂ H₅ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃; R^(o) ═R³ ═Y¹ ═Y^(1') ═H) was obtained as a pale yellow solid meltingover the range of 176°-179° C.

EXAMPLE 453,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-butoxycarbonylphthalide

(Formula VI: R¹ ═R² ═H/COO(CH₂)₃ CH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂CH₃ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H) was obtained as a light orange solidmelting at 88° C. with decomposition.

EXAMPLE 463,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide

(Formula VI: R¹ ═R² ═H/COO(CH₂)₇ CH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂CH₃ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H) was obtained as an orange oil.

EXAMPLE 473,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide

(Formula VI: R¹ ═R² ═H/COOCH₂ C₆ H₅ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂CH₃ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H) was obtained as a light orange solidmelting over the range of 94°-100° C. with decomposition.

EXAMPLE 483,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-allyloxycarbonylphthalide

(Formula VI: R¹ ═R² --H/COOCH₂ CH═CH₂ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6')═CH₂ CH₃ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H) was obtained as a light orangesolid melting over the range of 75°-87° C.

EXAMPLE 493,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-hexadecyloxycarbonylphthalide

(Formula VI: R¹ ═R² --H/COO(CH₂)₁₅ CH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6')═CH₂ CH₃ ; R^(o) ═R³ ═Y¹ ═Y^(1') ═H) was obtained as a dark red oil.Infrared maxima appeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s).

EXAMPLE 50

Proceeding in a manner similar to that described in Example 13 above,4.43 g (0.01 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared as described in Example 2, part A above, was interactedwith 2.0 g (0.015 mole) of m-amino-N,N-dimethylaniline in the presenceof ten ml of acetic anhydride to obtain3-[2-acetamido-4-dimethylaminophenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; ##STR34## R⁶ ═CH₂ CH₃ ;Y¹ ═H) which developed a blue-green color when spotted on silica gel inthe form of a toluene solution.

EXAMPLE 51

Following a procedure similar to that described in part B of Example 2above, 4.45 g (0.01 mole) of2-(1-ethyl-2-methyl-3-indolyl)carbonyl-3,4,5,6-tetrachlorobenzoic acidand 2.20 g (0.01 mole) of N,N,N',N'-tetraethyl-m-phenylenediamine wereinteracted in the presence of ten ml of acetic anhydride to obtain3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁶ ═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ;R⁵ ═CH₃ ; Y¹ ═H) melting at 100°-103° C. and showing a significantinfrared absorption maxima at 1770 cm⁻¹ (C═O; s). A toluene solution ofthis compound developed an intense blue color when spotted on silicagel.

EXAMPLE 52

Employing a procedure similar to that described in part C of Example 1,9.72 g (0.04 mole) of 2-(1,2-dimethyl-3-indolyl)-carbonylbenzoic acidprepared as described in U.S. Pat. No. 3,509,173, 8.57 g (0.05 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 6.0 ml of acetic anhydrideare interacted to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolylphthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═R⁶ ═CH₃ ; R⁴ ═N(CH₃)₂).

EXAMPLE 53

A. Employing a procedure similar to that described in part A of Example10 above, 7.15 g (0.025 mole) of tetrachlorophthalic anhydride and 3.65g (0.028 mole) of 2-methylindole were interacted in 100 ml of ethylenedichloride to obtain2-[2-methyl-3-indolyl)carbonyl]-4,5,6,7-tetrachlorobenzoic acid (FormulaVIII: R^(o) ═R¹ ═R² ═R³ ═Cl; R⁵ ═CH₃ ; R⁶ ═Y¹ ═H), an orange solidmelting at 200°-201° C.

B. A stirred mixture of 4.17 g of2-[(2-methyl-3-indolyl)carbonyl]-4,5,6,7-tetrachlorobenzoic acid,prepared as described in part A above and 3.28 g (0.02 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine were interacted in the presenceof 40 ml of acetic anhydride after the manner described in Example 2,part B above to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═Y¹═H) which showed an infrared carbonyl absorption maximum at 1775 cm⁻¹. Atoluene solution of the compound developed a blue-black color whenspotted on silica gel.

EXAMPLE 54

Proceeding in a manner similar to that described in part B of Example 5above, 2.34 g (0.006 mole) of2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]benzoic acid preparedaccording to Example 5, part A, and 2.40 g ofN,N,N',N'-tetraethyl-m-phenylenediamine were interacted in the presenceof 2.40 g of acetic anhydride to obtain3-[2,4-bis(diethylamino)phenyl]-3-(1-n-octyl-2-methyl-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═Y¹ ═H; R═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ; R⁵═CH₃ ; R⁶ ═(CH₂)₇ CH₃) as a tar-like semisolid. A toluene solution ofthis material developed a purple color when spotted on silica gel.

EXAMPLE 55

A. Proceeding in a manner similar to that described in part A of Example10, 29.6 g (0.20 mole) of phthalic anhydride and 35.2 g (0.20 mole) of5-nitro-2-methylindole were interacted in 100 ml of ethylene dichlorideto obtain 2-[(2-methyl-5-nitro-3-indolyl)carbonyl]benzoic acid (FormulaVIII: R^(o) ═R¹ ═R² ═R³ ═R⁶ ═H; R⁵ ═CH₃ ; Y¹ ═5-NO₂), a red brown solidmelting at 144°-148° C. and showing a strong carbonyl absorption maximumat 1700 cm⁻¹ in the infrared spectrum.

B. Following a procedure similar to that described in part B of Example18 for interacting 3.24 g (0.01 mole) of2-[(2-methyl-5-nitro-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, and 1.6 g (0.01 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine in the presence of 5.0 ml ofacetic anhydride, there is obtained3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-5-nitro-3-indolyl)phthalide(Formula III: R^(o) ═R¹ ═R² ═R³ ═R⁶ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹═NO₂).

EXAMPLE 56

A. Using a procedure similar to the one described in part A of Example18, 48.0 g (0.25 mole) of trimellitic anhydride and 32.8 g (0.25 mole)of 2-methylindole were interacted in 250 ml of ethylene dichloride toobtain 66.1 g of 4/5-carboxy-2-[(2-methyl-3-indolyl)carbonyl]benzoicacid (Formula VIII: R¹ ═R² ═H/COOH; R^(o) ═R³ ═R⁶ ═Y¹ ═H; R⁵ ═CH₃)melting at 237°-241° C.

B. A procedure similar to that described in part B of Example 18 above,was followed for interacting 10 g (0.023 mole) of4/5-carboxy-2-[(2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, and 8.0 g (0.06 mole) of 2-methylindole inthe presence of 50 ml of acetic anhydride. There was thus obtained3,3-bis(2-methyl-3-indolyl)-5/6-carboxyphthalide (Formula VI: R¹ ═R²═H/COOH; R^(o) `R³ ═R⁶ ═R^(6') ═Y¹ ═Y^(1') ═H; R⁵ ═R^(5') ═CH₃), a pinksolid melting over the range of 145°-165° C.

EXAMPLE 57

A. Proceeding in a similar fashion to the one described in part A ofExample 17, 28.6 g (0.01 mole) of tetrachlorophthalic anhydride, 16.2 g(0.2 mole) of N-methylpyrrole and 40 g (0.3 mole) of aluminum chloridewere interacted in 50 ml of dry chlorobenzene to obtain2-[(1-methyl-2-pyrrolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acid(Formula IX: R^(o) ═R¹ ═R² ═R³ ═Cl; R⁷ ═CH₃) having a melting point of203°-205° C.

B. Employing the procedure of part B of Example 17 hereinabove, 3.70 g(0.01 mole) of2-[(1-methyl-2-pyrrolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acid,prepared as described in part A above, and 2.0 g (0.012 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine were interacted in the presenceof 10 ml of acetic anhydride to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-methyl-2-pyrrolyl)-4,5,6,7-tetrachlorophthalide(Formula IV: R^(o) ═R¹ ═R² ═R³ ═Cl; R═R⁷ ═CH₃ ; R⁴ ═N(CH₃)₂).

EXAMPLE 58

To a stirred solution of 5.3 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,prepared as described in Example 22, part A, in 25 ml of acetone, therewas added 30 ml of a 0.5 N methanolic sodium hydroxide solution. Themixture was stirred for approximately fifteen minutes at ambienttemperature and concentrated to a syrup under vacuum. A small portion offresh acetone was added to the syrup and the dark blue crystals whichformed were collected by filtration. A small portion of hexane was addedto the crystals resulting in a gummy residue. The residue was thentriturated with more hexane to obtain a bright blue powder which wascollected by filtration and dried to yield 4.8 g of the sodium salt of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R^(o) ═R³ ═Y¹ ═H; R¹ ═R² ═H/COO.sup.⊖ Na.sup.⊕ ; R═R⁶ ═C₂H₅ ; R⁴ ═OC₂ H₅ ; R⁵ ═CH₃), a bright blue colored powder melting overthe range 82°-95° C. Infrared spectral analysis showed significantmaxima at 1752 (C═O, s) and 1735 cm⁻¹ (C═O, s).

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate2-{[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]carbonyl}-3-R^(o) -4-R¹ -5-R² -6-R³-benzoic acids of Formula VIII and appropriately substituted 3-R⁴-N,N-(R)₂ -anilines there will be obtained the 3-[2-R⁴ -4-N(R)₂-phenyl]-3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-4-R^(o) -5-R¹ -6-R² -7-R³-phthalides of Formula III, Examples 59-75, presented in Table Ahereinbelow.

    TABLE A      Phthalides of Formula III Ex. R R.sup.0 R.sup.1 R.sup.2 R.sup.3 R.sup.4 R     .sup.5 R.sup.6 Y.sup.1       59 n-C.sub.4 H.sub.9 H H N(C.sub.2 H.sub.5).sub.2 H N(n-C.sub.4     H.sub.9).sub.2 C.sub.2 H.sub.5 H 5-CH.sub.3 60 C.sub.6 H.sub.5 CH.sub.2     H H/COONHC.sub.8 H.sub.17 H/COONHC.sub.8 H.sub.17 H OC.sub.3 H.sub.7 H     C.sub.6 H.sub.5 CH.sub.2 5-F 61 C.sub.3 H.sub.7 H H H F N(C.sub.3     H.sub.7).sub.2 H CH.sub.3 6-NO.sub.2 62 CH.sub.3 H H/COO--i-C.sub.3     H.sub.7 H/COO--i-C.sub.3 H.sub.7 H Cl C.sub.2 H.sub.5 H 5,6-Cl.sub.2 63     4-Cl--C.sub.6 H.sub.4 CH.sub.2 H H/COO.sup.⊖ K.sup.⊕     H/COO.sup.⊖ K.sup.⊕ H C.sub.3 H.sub.7 CH.sub.3 2-CH.sub.3     --1-C.sub.3 H.sub.4 H 64 i-C.sub.3 H.sub.7 H I H H N(i-C.sub.3 H.sub.7)     CH.sub.3 2,6-(Cl).sub.2 C.sub.6 H.sub. 3 CH.sub.2 H 65 CH.sub.3 H Br Br     H N(CH.sub.3).sub.2 H H 5,6(OCH.sub.3).sub.2 66 4-CH.sub.3 --C.sub.6     H.sub.4 CH.sub.2 H H/COON(C.sub.2 H.sub.5).sub.2 H/COON(C.sub.2      H.sub.5).sub.2 H OC.sub.4 H.sub.9 H i-C.sub.5 H.sub.11 H 67 i-C.sub.4     H.sub.9 Br Br Br Br N(i-C.sub.4 H.sub.9).sub.2 CH.sub.3 C.sub.2 H.sub.3     H 68 2-F--C.sub.6 H.sub.4 CH.sub.2 H H/COO.sup.⊖      NH.sub.4.sup.⊕ H/COO.sup.⊖ NH.sub.4.sup.⊕ H Br C.sub.2     H.sub.5 H 5-CH.sub.3 69 2,5(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2 H     N(n-C.sub.4 H.sub.9).sub.2 H H NHCOCH.sub.3 H 1-CH.sub.3 C.sub.6     H.sub.12 5-I 70 C.sub.2 H.sub.5 H H/COON(CH.sub.2).sub.8      --CH(CH.sub.3).sub.2 H/COON(CH.sub.2).sub.8 --CH(CH.sub.3).sub.2 H     OCH.sub.3 C.sub.3 H.sub.7 H H 71 C.sub.6 H.sub.4      CH.sub.2 H H/COOCH.sub.2 C.sub.6 H.sub.4 Cl H/COOCH.sub.2 C.sub.6     H.sub.4 ClHI CH.sub.3 H 5,6(CH.sub.3).sub.2 72 CH.sub.3 H H/COONC.sub.6     H.sub.13 H/COONC.sub.6 H.sub.13 H O--i-C.sub.3 H.sub.7 CH.sub.3 H 6-Br     73 n-C.sub.4 H.sub.9 H H/COO.sup.⊖.sup.⊕NHCH.sub.3 C.sub.14     H.sub.29 H/COO.sup.⊖.sup.⊕NHCH.sub.3 C.sub.14 H.sub.29 H     C.sub.2 H.sub.5 CH.sub.3 2-F--C.sub.6 H.sub.4 CH.sub.2 H 74 C.sub.2     H.sub.5 H H/COOCH.sub.2 C.sub.6 H.sub.3 --(CH.sub.3).sub.2 H/COOCH.sub.2     C.sub.6 H.sub.3 --(CH.sub.3).sub.2 H OC.sub.4 H.sub.9 H CH.sub.3     5-Br--6-NO.sub.2 75 C.sub.6 H.sub.5 CH.sub.2, CH.sub.3 H H/COONHC.sub.2     H.sub.4 N(CH.sub.3).sub.2 H/COONHC.sub.2 H.sub.4 N(CH.sub.3).sub.2 H     C.sub.2 H.sub.5 CH.sub.3 C.sub.2      H.sub.5 H

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate2-(1-R⁷ -2-pyrrolyl)carbonyl-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acids ofFormula IX and appropriately substituted 3-R⁴ -N,N-(R)₂ -anilines therewill be obtained the 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(1-R⁷-2-pyrrolyl)-4-R^(o) -5-R¹ -6-R² -7-R³ -phthalides of Formula IV,Examples 76-87, presented in Table B hereinbelow.

                                      TABLE B                                     __________________________________________________________________________    Phthalides of Formula IV                                                      Ex.                                                                              R         R.sup.0                                                                         R.sup.1    R.sup.2    R.sup.3                                                                         R.sup.4                                                                             R.sup.7                          __________________________________________________________________________    76 n-C.sub.4 H.sub.9                                                                       H H          N(C.sub.2 H.sub.5).sub.2                                                                 H N(n-C.sub.4 H.sub.9).sub.2                                                          C.sub.6 H.sub.5                  77 2,4-Cl.sub.2 --C.sub.6 H.sub.3 CH.sub.2                                                 H H/C00.sup.⊖ Li.sup.⊕                                                         H/COO.sup.⊖ Li.sup.⊕                                                         H OC.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                  78 C.sub.2 H.sub.5                                                                         H Br         H          H N(C.sub.2 H.sub.5).sub.2                                                            i-C.sub.3 H.sub.7                79 i-C.sub.3 H.sub.7                                                                       Br                                                                              Br         Br         Br                                                                              N(i-C.sub.3 H.sub.7).sub.2                                                          C.sub.2 H.sub.5                  80 4-BrC.sub.6 H.sub.4 CH.sub.2                                                            H H/COOC.sub.10 H.sub.21                                                                   H/COOC.sub.10 H.sub.21                                                                   H Cl    CH.sub.3                         81 2-F--C.sub.6 H.sub.4 CH.sub.2                                                           H H/COONHC.sub.12 H.sub.23                                                                 H/COONHC.sub.12 H.sub.23                                                                 H OCH.sub.3                                                                           n-C.sub.3 H.sub.7                82 2,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                           H H/COON(n-C.sub.4 H.sub.9).sub.2                                                          H/COON(n-C.sub.4 H.sub.9).sub.2                                                          H I     C.sub.6 H.sub.5                  83 C.sub.6 H.sub.5 CH.sub.2, s-C.sub.4 H.sub.9                                             H H/COO.sup.⊖ .sup.⊕NH.sub.3 C.sub.18 H.sub.37                                 H/COO.sup.⊖ .sup.⊕NH.sub.3 C.sub.18                               H.sub.37   H C.sub.3 H.sub.7                                                                     C.sub.2 H.sub.5                  84 C.sub.2 H.sub.5                                                                         Cl                                                                              Cl         Cl         Cl                                                                              N(C.sub.2 H.sub.5).sub.2                                                            i-C.sub.3 H.sub.7                85 C.sub.6 H.sub.4 CH.sub.2                                                                H NO.sub.2   H          H NHCOCH.sub.3                                                                        C.sub.6 H.sub.5                  86 n-C.sub.3 H.sub.7                                                                       H NHCOCH.sub.3                                                                             H          H Br    C.sub.2 H.sub.5                  87 CH.sub.3  H H/COONHC.sub.2 H.sub.4 --                                                                H/COONHC.sub.2 H.sub.4 --                                                                H CH.sub.3                                                                            CH.sub.3                                        N(i-C.sub.3 H.sub.7).sub.2                                                               N(i-C.sub.3 H.sub.7).sub.2                          __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate2-(9-R⁸ -3-carbazolyl)carbonyl-3-R^(o) -4-R¹ -5-R² -6-R³ -benzoic acidsand appropriately substituted 3-R⁴ -N,N-(R)₂ -anilines there will beobtained the 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(9-R⁸ -3-carbazolyl)-4-R^(o)-5-R¹ -6-R² -7-R³ -phthalides of Formula V, Examples 88-98, presented inTable C hereinbelow.

                                      TABLE C                                     __________________________________________________________________________    Phthalides of Formula V                                                       Ex.                                                                             R         R.sup.0                                                                         R.sup.1      R.sup.2      R.sup.3                                                                         R.sup.4                                                                             R.sup.8                       __________________________________________________________________________    88                                                                              C.sub.6 H.sub.5 CH.sub.2                                                                H H/COOH       H/COOH       H Cl    i-C.sub.3 H.sub.7             89                                                                              n-C.sub.3 H.sub.7                                                                       Cl                                                                              Cl           H            Cl                                                                              N(n-C.sub.3 H.sub.7).sub.2                                                          C.sub.6 H.sub.5               90                                                                              C.sub.6 H.sub.5 CH.sub.2, C.sub.2 H.sub.5                                               H H/COO--n-C.sub.4 H.sub.9                                                                   H/COO--n-C.sub.4 H.sub.9                                                                   H H     C.sub.2 H.sub.5               91                                                                              3-Cl--C.sub.6 H.sub.4 CH.sub.2                                                          H H/COO.sup.⊖ Na.sup.⊕                                                           H/COO.sup.⊖ Na.sup.⊕                                                           H I     n-C.sub.3 H.sub.7             92                                                                              i-C.sub.4 H.sub.9                                                                       H H/COONHC.sub.16 H.sub.33                                                                   H/COONHC.sub.16 H.sub.33                                                                   H NHCOCH.sub.3                                                                        CH.sub.3                      93                                                                              C.sub.2 H.sub.5                                                                         Br                                                                              Br           Br           Br                                                                              N(C.sub.2 H.sub.5).sub.2                                                            i-C.sub.3 H.sub.7             94                                                                              2,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                           H H/COOC.sub.2 H.sub.3                                                                       H/COOC.sub.2 H.sub.3                                                                       H O--i-C.sub.3 H.sub.7                                                                C.sub.2 H.sub.5               95                                                                              2-F--C.sub.6 H.sub.4 CH.sub.2                                                           H H/COO.sup.⊖ .sup.⊕NH.sub.3 C.sub.6 H.sub.13                                    H/COO.sup.⊖ .sup.⊕NH.sub.3 C.sub.6                                H.sub.13     H Br    C.sub.2 H.sub.5               96                                                                              2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2                                                   H H/COON(C.sub.18 H.sub.37).sub.2                                                            H/COON(C.sub.18 H.sub.37).sub.2                                                            H C.sub.3 H.sub.7                                                                     i-C.sub.3 H.sub.7             97                                                                              4-Cl--C.sub.6 H.sub.8 CH.sub.2                                                          H H/COOC.sub.12 H.sub.25                                                                     H/COOC.sub.12 H.sub.25                                                                     H Cl    CH.sub.3                      98                                                                              n-C.sub.3 H.sub.7                                                                       H H/COONHC.sub.3 H.sub.7 N(CH.sub.3).sub.2                                                   H/COONHC.sub.3 H.sub.7 N(CH.sub.3).sub.2                                                   H CH.sub.3                                                                            C.sub.6 H.sub.5               __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate2-{[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]carbonyl}-3-R^(o) -4-R¹ -5-R² -6-R³-benzoic acids of Formula VIII and appropriately substituted 1-R^(6')-2-R^(5') -5/6-Y^(1') -indoles there will be obtained the 3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5') -5/6-Y¹)-3-indolyl]-4-R^(o)-5-R¹ -6-R² -7-R³ -phthalides of Formula VI, Examples 99-112, presentedin Table D hereinbelow.

                                      TABLE D                                     __________________________________________________________________________    Phthalides of Formula VI                                                      Ex.                                                                              R.sup.0                                                                         R.sup.1 /R.sup.2                                                                           R.sup.3                                                                         R.sup.5                                                                           R.sup.6  Y.sup.1                                                                             R.sup.5'                                                                         R.sup.6'  Y.sup.1'                  __________________________________________________________________________     99                                                                              H H/COO.sup.⊖ K.sup.⊕                                                            H H   H        H     H  C.sub.4 H.sub.9                                                                         OCH.sub.3                 100                                                                              H H/COOC.sub.18 H.sub.37                                                                     H H   C.sub.6 H.sub.4 CH.sub.2                                                               5-F   C.sub.6 H.sub.5                                                                  H         H                         101                                                                              H H/COONHC.sub.6 H.sub.13                                                                    H H   CH.sub.3 6-NO.sub.2                                                                          C.sub.2 H.sub.5                                                                  H         CH.sub.3                  102                                                                              H H/COO.sup.⊖ .sup.⊕NH(CH.sub.3).sub.3                                           H i-C.sub.3 H.sub.7                                                                 H        H     H  CH.sub.3  5-Br, 6-NO.sub.2          103                                                                              H H/COONH.sub.2                                                                              H CH.sub.3                                                                          H        6-Br  CH.sub.3                                                                         2,5-(CH.sub.3).sub.2 C.sub.6                                                  H.sub.3 CH.sub.2                                                                        H                         104                                                                              H H/COOC.sub.14 H.sub.29                                                                     H CH.sub.3                                                                          2-(C.sub.2 H.sub.5)C.sub.6 H.sub.12                                                    H     CH.sub.3                                                                         C.sub.2 H.sub.3                                                                         H                         105                                                                              H H/COON(CH.sub.3).sub.2                                                                     H i-C.sub.3 H.sub.7                                                                 4-BrC.sub.6 H.sub.4 CH.sub.2                                                           H     H  H         5,6-(CH.sub.3).sub.2      106                                                                              H H/COO(CH.sub.2).sub.8 CH(CH.sub.3).sub.2                                                   H H   i-C.sub.5 H.sub.11                                                                     H     C.sub.6 H.sub.5                                                                  H         5,6-(Cl).sub.2            107                                                                              H H/COO.sup.⊖ .sup.⊕NH.sub.4                                                     H CH.sub.3                                                                          2-CH.sub.3 --C.sub.6 H.sub.4 CH.sub.2                                                  H     H  1-CH.sub.3 --C.sub.6 H.sub.12                                                           5-I                       108                                                                              H H/COOCH.sub.2 C.sub.6 H.sub.4 Cl                                                           H CH.sub.3                                                                          3-(2-CH.sub.3)--1-C.sub.3 H.sub.3                                                      H     CH.sub.3                                                                         2,5-(CH.sub.3).sub.2 C.sub.6                                                  H.sub.3 CH.sub.2                                                                        H                         109                                                                              H H/COOCH.sub.2 C.sub.6 H.sub.3 (CH.sub.3).sub.2                                             H CH.sub.3                                                                          i-C.sub.4 H.sub.9                                                                      H     CH.sub.3                                                                         C.sub.18 H.sub.37                                                                       H                         110                                                                              H H/COO[3-(2-CH.sub.3)--1C.sub.3 H.sub.3 ]                                                   H CH.sub.3                                                                          H        5,6-(CH.sub.3).sub.2                                                                C.sub.2 H.sub.5                                                                  3-Cl--C.sub.6 H.sub.4 CH.sub.2                                                          H                         111                                                                              H H/COOC.sub.6 H.sub.13                                                                      H CH.sub.3                                                                          2-F--C.sub.6 H.sub.4 CH.sub.2                                                          H     CH.sub.3                                                                         CH.sub.3  6-NO.sub.2                112                                                                              H H/COONHC.sub.6 H.sub.12 N(CH.sub.3).sub.2                                                  H C.sub.2 H.sub.5                                                                   H        CH.sub.3                                                                            CH.sub. 3                                                                        C.sub.2 H.sub.5                                                                         H                         __________________________________________________________________________

EXAMPLE 113

Proceeding in a manner similar to that described in Example 18, part Babove 3.5 g (0.01 mole) of the4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl] benzoic acid,prepared as described in Example 18, part A above, 1.65 g (0.01 mole) ofN,N-diethyl-3-hydroxyaniline and 15.0 ml of acetic anhydride wereinteracted at ambient temperature for four hours to obtain 5.8 g of3-(2-acetyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R⁰ ═R³ ═Y² ═H; R¹ ═R² ═H/COOH, R⁴ ═CH₃ COO; R⁶═CH₂ CH₃) as a blue solid melting over the range 108°-138° C. Infraredmaxima appeared at 1770 (C═0; s) and 1730 cm⁻¹ (C═0; s).

EXAMPLE 114

Proceeding in a manner similar to that described in Example 28, part Babove substituting bromohexadecane for dimethylsulfate, there wasobtained3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-hexadecyloxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R^(o) ═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COO(CH₂)₁₅ CH₃; R⁶ ═C₂ H₅) a light yellow-green oil. Infrared maxima appeared at 1775C═0; s) and 1735 cm⁻¹ (C═0; s).

EXAMPLE 115

The use of the compounds of Formulas I through VI and described inExamples 1 through 114 as color forming components in pressure sensitivemicroencapsulated copying systems is illustrated with reference to theproduct of Example 1, part B.

A. A mixture of 196 ml of distilled water and 15.0 g of pigskin gelatinwas stirred at approximately 50° C. for approximately 45 minutes. Therewas then added to the mixture a warmed (approximately 50° C.) solutionof 49.0 g of alkylated biphenyls and 0.5 g of3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide,prepared as described above in Example 1, part B. The resulting solutionwas stirred for approximately fifteen minutes. A second solution of 81.0ml of distilled water and 10.0 g of gum arabic was then prepared andwarmed to approximately 50° C. for approximately one hour.

B. The two solutions, the first containing water, gelatin, alkylatedbiphenyls and the product, and the second containing water and gumarabic were mixed and the pH adjusted to 9 by the addition ofapproximately 0.7 ml of 20 percent aqueous sodium hydroxide. Theresulting mixture was transferred to a larger reactor equipped with avariable speed one-half horsepower Eppenbach Homo-Mixer (Gifford-WoodCo., Hudson, N.Y.) and there was added over a period of two to threeminutes 650 ml of distilled water which had been heated to 50° C. Withthe stirrer running at an applied voltage of between 20 to 25 voltsthere was slowly added sufficient ten percent aqueous acetic acid to setthe pH at 4.5, this being the point where coacervation was initiated.The stirrer speed was increased by raising the applied voltage toapproximately thirty volts and approximately four drops of2-ethylhexanol were added to suppress foaming. After approximatelytwenty minutes, a sample of the suspension was examined microscopicallyand found to have stabilized in the range of 20 to 25 microns particlesize whereupon an external ice/water bath was immediately placed aroundthe reactor containing the suspension. At approximately 20° C., theagitation speed was reduced by decreasing the applied voltage to therange of 20 to 25 volts. Cooling was continued and at approximately 15°C., 10.0 ml of glutaraldehyde was added over a period of five minutes.When the internal temperature reached 10° C., the agitation speed wasfurther reduced by lowering the applied voltage to approximately 20volts and these conditions maintained for approximately thirty minutes.At this time, the Eppenbach Homo-Mixer was replaced with a conventionalblade type laboratory agitator and the suspension was stirred anadditional three hours during which period the temperature was allowedto warm to room temperature. The microencapsulated product was isolatedby pouring the slurry through as ASTM #18 stainless steel sieve toremove any large agglomerates and then collecting the capsules byfiltration. The collected capsules wer washed successively with four 100ml portions of distilled water each and stored as a water wet pulp. Asample of the pulp analyzed by drying in vacuo at 80° C. was found toconsist of 37.5 percent solids.

C. To 125 ml of distilled water, 10.6 g of oxidized corn starch wasadded over a period of ten to fifteen minutes with stirring. Thismixture was heated to a temperature in the range of 70°-80° C. andmaintained until all the starch dissolved. The starch solution wascooled to ambient temperature and there was added 100 g of thecapsule-containing water wet pulp from part B above and 43.0 ml ofdistilled water. The capsules and starch solution were mixed at roomtemperature using an Eppenbach Homo-Mixer set at an applied voltage of25 volts for five minutes and then at an applied voltage of 30 volts foran additional five minutes to complete the suspension of the capsules inthe starch solution.

D. The stock starch-microcapsule suspension prepared in part C above wascoated on paper sheets to a thickness of approximately 0.0015 inch andthe coated paper air dried. The paper thus coated with themicroencapsulated colorless precursor was assembled as the top sheet ina manifold system by positioning the coated side in contact with thecoated side of a commercially available receiving sheet coated with acolor developer of the electron accepting type. More specifically,papers coated with a phenolic resin and with an acidic clay wereemployed in this test. An image was then drawn with a stylus on the topsheet bearing the microencapsulated colorless precursor on its reverseside causing the affected microcapsules to rupture thus allowing thesolution of the colorless precursor held by said microcapsules to flowinto contact with the color developing substance on the receiving sheetwhereupon a deep blue-colored image promptly formed. The developed imageexhibited good lightfastness when exposed to daylight or to a daylightfluorescent lamp for extended periods.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 1, part C,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-phthalideproduced a grape-colored developed image.

EXAMPLE 116

The use of the compounds of Formulas I through VI and described inExamples 1 through 114 as color forming components in pressure sensitivemicroencapsulated copying systems is similarly illustrated withreference to the product of Example 23.

A. A mixture of 196 ml of distilled water and 15.0 g of pigskin gelatinwas stirred at approximately 50° C. for approximately 45 minutes. Therewas then added to the mixture a warmed (approximately 50° C.) solutionof 49.0 g of alkylated biphenyls and 1.0 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalideprepared as described above in Example 23. The resulting solution wasstirred for approximately fifteen minutes. A second solution of 81.0 mlof distilled water and 5.0 g of carboxymethylcellulose was then preparedand warmed to approximately 50° C. for approximately one hour.

B. The two solutions, the first containing water, gelatin, alkylatedbiphenyls and the product, and the second containing water withcarboxymethylcellulose were mixed by means of an Eppenbach Homo-Mixer(Gifford-Wood Co., Hudson, N.Y.). The pH was adjusted to 6.5 by theaddition of approximately 0.7 ml of 20 percent aqueous sodium hydroxide.To the resultant mixture was added over a period of two to three minutes650 ml of distilled water which had been heated to 50° C. With thestirrer running at an applied voltage of between 35 to 40 volts therewas slowly added sufficient ten percent aqueous acetic acid to set thepH at 4.5, this being the point where coacervation was initiated. Fourdrops of 2-ethylhexanol were added to suppress foaming. Afterapproximately twenty minutes an external ice/water bath was placedaround the reactor containing the suspension. Cooling was continued andat approximately 15° C., 10.0 ml of glutaraldehyde was added over aperiod of five minutes. When the internal temperature reached 10° C.,the Eppenbach Homo-Mixer was replaced with a conventional blade typelaboratory agitator and the thus prepared suspension of microcapsuleswas stirred an additional three hours during which period thetemperature was allowed to warm to room temperature.

C. The mcirocapsule suspension prepared as described in part B above wascoated on paper sheets to a thickness of approximately 0.0015 inch andthe coated paper air dried. The paper thus coated with themicroencapsulated colorless precursor was assembled as the top sheet ina manifold system by positioning the coated side in contact with thecoated side of a commercially available receiving sheet coated with acolor developer of the electron accepting type. More specifically,papers coated with a phenolic resin and with an acidic clay wereemployed in this test. An image was then drawn with a stylus on the topsheet bearing the microencapsulated colorless precursor on its reverseside causing the affected microcapsules to rupture thus allowing thesolution of the colorless precursor held by said microcapsules to flowinto contact with the color developing substance on the receiving sheetwhereupon a deep blue-colored image promptly formed. The developed imageexhibited good lightfastness when exposed to daylight or to a daylightfluorescent lamp for extended periods.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 29,3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide,produced a blue-colored developed image; the product of Example 34,3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide,produced a turquoise-colored developed image; the product of Example39B, 3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a deep red-colored developed image; the product of Example 2B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide,produced a deep grape-colored developed image; the product of Example3B, 3-[b2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide,produced a blue-black-colored image. EXAMPLE 117

When evaluated in a carbonless duplicating system by proceeding in amanner similar to that described in Example 116 above, except that soyoil was used in place of alkylated biphenyls, the product of Example 20,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide,produced a grape-colored developed image; and the product of Example 46,3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide,produced a deep red-colored developed image.

EXAMPLE 118

Following a procedure similar to that described in Example 116 but usingkerosene instead of alkylated biphenyls for evaluation in a carbonlessduplication system, the product of Example 26,3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-hexadecyloxycarbonylphthalide,produced a deep blue-colored developed image.

EXAMPLE 119

The utility of the phthalides of Formulas I to IV whose preparations aredescribed in the foregoing examples as color forming components inthermal marking systems is illustrated by the incorporation and testingof the compound of Example 22B,3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalidein a thermal sensitive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 3,539,375.

A. A mixture of 2.0 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,8.6 g of a ten percent aqueous solution of polyvinyl alcohol(approximately 99 percent hydrolyzed), 3.7 g of water and 31.6 g of 1/16inch diameter zirconium grinding beads was charged into a containerwhich was placed in a mechanical shaker. Shaking was effected for onehour. The zirconium beads were then removed by straining the mixturethrought a No. 40 sieve.

B. Similarly, a mixture of 9.8 g of 4,4'-isopropylidine diphenol(Bisphenol A), 42.0 g of a ten percent aqueous polyvinyl alcoholsolution (approximately 99 percent hydrolyzed), 18.2 g of water and221.2 g of 1/16 inch diameter zirconium grinding beads was charged intoa container which was placed in a mechanical shaker. After shaking waseffected for one hour, the zirconium beads were removed by strainingthrought a No. 40 sieve.

C. A coating composition was prepared by mixing 2.1 g of the slurry fromA and 47.9 g of the slurry from B. The mixture was then uniformly coatedon sheets of paper at thicknesses of approximately 0.003 inch and thecoated sheets air-dried. The coated paper was tested by tracing a designon the coated side of the paper placed on a smooth flat surface with astylus heated to approximately 125° C. A deep blue-colored imagecorresponding to the traced design promptly developed.

When evaluated in thermal marking paper prepared and tested as describedabove, the product of Example 39B,3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a violet-colored image; the product of Example 21,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide,produced a grape-colored image; the product of Example 28B,3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a blue-colored image; the product of Example 33B,3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a turquoise-colored image; the product of Example 1B,3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide,produced a blue-black-colored image; the product of Example 1C,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide,produced a grape-colored image; the product of Example 2B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide,produced a deep grape-colored developed image; the product of Example3B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide,produced a blue-black-colored image.

We claim:
 1. A 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(9-R⁸ -3-carbazolyl)-4-R^(o)-5-R¹ -6-R² -7-R³ -phthalide of the formula ##STR35## wherein: R^(o), R³and one of R¹ and R² represent hydrogen and the other of R¹ and R²represent ##STR36## in which B represents ##STR37## wherein Y ishydrogen, an alkali metal cation, an ammonium cation, a C₁ to C₁₈ mono-,di- or trialkylammonium cation, C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,benzyl or benzyl substituted in the benzene ring thereof by C₁ to C₁₂alkyl, halo or C₁ to C₈ alkoxy,Y' is hydrogen or C₁ to C₁₈ alkyl, and Y"is hydrogen, C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dimethylamino; Rrepresents non-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted inthe benzene ring by one or two of halo or C₁ to C₃ alkyl; R⁴ representshydrogen, C₁ to C₃ alkyl, C₁ to C₄ alkoxy, acetamido, dialkylamino inwhich alkyl is non-tertiary C₁ to C₄ alkyl, C₂ to C₅ acyloxy, or halo;and R⁸ represents hydrogen, C₁ to C₃ alkyl or phenyl.